AU2017327000B2

AU2017327000B2 - Anode apparatus and methods regarding the same

Info

Publication number: AU2017327000B2
Application number: AU2017327000A
Authority: AU
Inventors: Lance SWORTS
Original assignee: Elysis LP
Current assignee: Elysis LP
Priority date: 2016-09-19
Filing date: 2017-09-19
Publication date: 2023-06-15
Anticipated expiration: 2037-09-19
Also published as: BR112019005313A2; DK201970168A1; EA201990554A1; CA3037199A1; SA519401348B1; DK181019B1; AU2017327000A1; CA3037199C; BR112019005313B1; EP3516094A1; WO2018053515A1; CN109715862B; MY203895A; EP3516094A4; ZA201902264B; US20200063279A1; CN109715862A

Abstract

In some embodiments, an anode apparatus comprises: (a) an anode body comprising at least one outer sidewall, wherein the outer sidewall is configured to define a shape of the anode body, and to perimetrically surround a hole in the anode body, wherein the hole comprises an upper opening in a top surface of the anode body and wherein the hole axially extends into the anode body; (b) a pin comprising: a first end and a second end opposite the first end, wherein the second end extends downward into the upper end of the anode body and into the hole of the anode body; and (c) a sealing material configured to cover at least a portion of at least one of the following: (1) an inner sidewall of the anode body; (2) the top surface of the anode body; (3) the pin; and (4) the anode support.

Description

ANODE APPARATUS AND METHODS REGARDING THE SAME CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit of U.S. provisional

application No. 62/396,583, filed September 19, 2016, which is

herein incorporated by reference in its entirety

BACKGROUND

[0001a] A reference herein to a patent document or any other

matter identified as prior art, is not to be taken as an

admission that the document or other matter was known or that

the information it contains was part of the common general

knowledge as at the priority date of any of the claims.

[0001b] Where any or all of the terms "comprise",

"comprises", "comprised" or "comprising" are used in this

specification (including the claims) they are to be interpreted

as specifying the presence of the stated features, integers,

steps or components, but not precluding the presence of one or

more other features, integers, steps or components.

[0002] An inert anode is electrically connected to the

electrolytic cell, such that a conductor rod is connected to

the inert anode in order to supply current from a current

supply to the inert anode, where the inert anode directs

current into the electrolytic bath to produce non-ferrous metal

(where current exits the cell via a cathode). In some

embodiments, during operation of the cell, corrosive bath

and/or vapor interacts with the anode assembly and can impact

the effectiveness and longevity of the anode assembly (e.g. by

weakening the mechanical connection, and/or increasing

resistivity at the electrical connection).

FIELD OF THE INVENTION

[0003] Generally, the instant disclosure is directed towards

an inert anode apparatus. More specifically, the instant

disclosure is directed towards an inert anode apparatus

configured to reduce, prevent, and/or eliminate corrosion of

the pin and/or anode material (e.g. by corrosive vapors and/or

molten electrolyte) in an electrolysis cell.

SUMMARY OF THE DISCLOSURE

[0004] Without being bound by a particular mechanism or

theory, it is believed that one or more embodiments of the

anode-pin-protective sealing material connection in the instant

disclosure provide enhanced corrosion resistance to the anode

assembly when measured in at least one of the following

locations: (a) at the pin, inside the hole in the anode body;

(b) at the anode body, along the inner diameter of the hole for

the anode pin; and/or (c) in the vapor zone where the pin

extends above the anode body (i.e., above the bath, and/or in

the refractory package).

[0005] Without being bound by a particular mechanism or

theory, it is believed that when the sealing material is

utilized in the anode assembly, it provides protection to (1)

mechanical attachment site of the anode to pin and/or (2) the

anode assembly components (e.g. pin, anode body, filler

material, cement material) as the sealing material is

configured to accept reactive fluoride species that are present

in situ in the bath and/or bath vapor. Without being bound by a

particular mechanism or theory, it is believed that by

undergoing the chemical transformation to accept the fluoride

species, the sealing material is transformed (at least

partially) from a solid to a liquid material. In some

embodiments, a sealing material is configured to extend between the inner surface of the hole in the anode body and the outer diameter of the pin.

[0006] One aspect of the instant disclosure provides an inert anode assembly, comprising: an anode support; and an inert anode apparatus mechanically attached to the anode support, wherein the inert anode apparatus comprises: (a) an inert anode body comprising at least one outer sidewall, wherein the outer sidewall is configured to define a shape of the inert anode body, and to perimetrically surround a hole in the inert anode body, wherein the hole comprises an upper opening in a top surface of the inert anode body and wherein the hole axially extends into the inert anode body; (b) a pin comprising: a. a first end connected to a current supply, and b. a second end opposite the first end, wherein the second end extends downward into the upper end of the inert anode body and into the hole of the inert anode body; (c) a filler material inside the hole and configured to electrically connect the anode body to the pin, wherein the filler material is retained in the hole between an inner sidewall of the inert anode body and the pin; and (d) a sealing material configured to reduce, prevent and/or eliminate corrosion of the inert anode apparatus, the sealing material comprising an aggregate selected from anode-matched aggregate and/or off-gas compatible aggregate, and a matrix, wherein the sealing material is bonded to the top surface of the anode body and configured to cover the top surface of the anode body and at least a portion of at least one of the following: (1) the inner sidewall of the inert anode body; (2) the filler material; (3) the pin; and (4) the anode support; and wherein at least a portion of the sealing material is retained above the top surface of the inert anode body; wherein the sealing material is configured to enclose the filler material into the inert anode body between the inner sidewall of the inert anode body and the pin; wherein the sealing material comprises a castable ceramic or cermet including A1 2 03 ,

SiO 2 , MgO, CaO, Na20, or combinations thereof, wherein the castable ceramic or castable cermet comprises at least aluminates

Page 2a of 38 and/or silicates, and said at least some of silicates and/or aluminates of said castable ceramic or castable cermet are replaced with an anode-matched aggregate and/or off-gas compatible aggregate specifically tailored to match the inert anode body; and wherein said anode-matched aggregate and/or off gas compatible aggregate comprises: aggregates comprising hematite or magnetite, wherein said inert anode body comprises hematite or magnetite; aggregates having a composition comprising at least one major compound of the inert anode body, said major compound comprising more than 30 wt.% of the composition of the inert anode body; or aggregates having a component of an off-gas compatible aggregate selected from NiFe204, NiO, CuAl20 4 , and CuO.

Page 2b of 38

[0007] In some embodiments of the instant disclosure, the sealing material comprises at least

one of. water, polymers, organics, dispersants, or diluents.

[0008] In some embodiments of the instant disclosure, a sealing material is configured to

cover at least a portion of at least one of the following: (1) an inner sidewall of the anode body;

(2) the pin; and (3) a filler material.

[0009] In some embodiments of the instant disclosure, the first end of the pin is configured to

be retained within an anode support.

[0010] In some embodiments of the instant disclosure, the filler is retained in the hole

between the inner sidewall of the anode body and the pin.

[0011] In some embodiments of the instant disclosure, the sealing material is configured to

enclose the conductive filler into the anode body between the inner sidewall of the anode body

and the pin.

[0012] In some embodiments of the instant disclosure, the sealing material is cast in place.

[0013] In some embodiments of the instant disclosure, the sealing material is pre-cast and

screwed into the anode body.

[0014] In some embodiments of the instant disclosure, the sealing material is sintered into

place during the sintering of the green form anode body into the final anode body.

[0015] In some embodiments of the instant disclosure, the sealing material is retained above

the top surface of the anode body.

[0016] In some embodiments of the instant disclosure, the sealing material is retained in the

hole.

[0017] In some embodiments of the instant disclosure, above the top surface of the anode

body includes extending along the pin.

[0018] In some embodiments of the instant disclosure, above the top surface of the anode

body includes extending along the pin and into the anode support.

[0019] In some embodiments of the instant disclosure, above the top surface includes

extending across the top surface of the upper portion of the anode body.

[0020] In some embodiments of the instant disclosure, above the top surface includes

extending across the top surface and extending down around the outer sidewall of the anode

body.

[0021] In some embodiments of the instant disclosure, the sealing material is applied to the

anode hole between the pin and the inner surface of the anode body in a gradient, such that the

concentration of sealing material varies in a radial direction.

[0022] In some embodiments of the instant disclosure, the gradient is configured such that

the concentration of sealing material is higher adjacent to the pin as compared to adjacent to the

inner surface of the anode body.

[0023] In some embodiments of the instant disclosure, the gradient is configured such that

the concentration of sealing material is lower adjacent to the pin as compared to adjacent to the

inner surface of the anode body.

[0024] In some embodiments of the instant disclosure, the sealing material is applied to the

concentration of sealing material varies in a lateral direction.

[0025] In some embodiments of the instant disclosure, the gradient is configured such that

the concentration of sealing material is higher adjacent to the upper end as compared to

adjacent to the lower end of the anode body.

[0026] In some embodiments of the instant disclosure, the

gradient is configured such that the concentration of sealing

material is lower adjacent to the upper end as compared to

adjacent to the lower end of the anode body.

[0027] In some embodiments of the instant disclosure, the sealing

material is configured with a higher concentration at a position

adjacent to the bath-vapor interface, as compared to either the

upper end in the vapor phase or the lower end in the bath of the

anode body.

[0028] In some embodiments of the instant disclosure, the

concentration of sealing material from a position just below the

bath-vapor interface to a position adjacent to the upper end of

the anode is higher than the portion of sealing material in the

submerged portion of the anode body.

[0029] One aspect of the instant disclosure provides an

electrolysis cell, comprising: a cell structure comprising a cell

bottom and a cell sidewall, wherein the cell sidewall is

configured to perimetrically surround the cell bottom and extend

in an upward direction from the cell bottom to define a control

volume, wherein the control volume is configured to retain a

molten electrolyte bath; and an inert anode assembly configured

to direct current into the molten electrolyte bath, wherein the

inert anode assembly comprises: an anode support; and an inert

anode apparatus mechanically attached to the anode support,

wherein the inert anode apparatus comprises: (a) an inert anode

body comprising at least one outer sidewall, wherein the outer

sidewall is configured to define the anode shape and to

perimetrically surround a hole in the inert anode body, wherein

the hole comprises an upper opening in a top surface of the

inert anode body and wherein the hole axially extends into the

inert anode body; (b) an pin comprising: a first end connected

to a current supply, and a second end opposite the first end,

wherein the second end is configured to extend down into the upper end of the inert anode body and into the hole of the inert anode body; (c) a filler material inside the hole and configured to electrically connect the anode body to the pin, wherein the filler material is retained in the hole between an inner sidewall of the inert anode body and the pin; and (d) a sealing material configured to reduce, prevent and/or eliminate corrosion of the inert anode apparatus, the sealing material, and comprising an aggregate selected from anode-matched aggregate and/or off-gas compatible aggregate, and a matrix, the sealing material being bonded to the top surface of the anode body and configured to cover the top surface of the anode body and at least a portion of at least one of the following: an inner sidewall of the inert anode body; the filler material; the pin; and the anode support; and wherein at least a portion of the sealing material is retained above the top surface of the inert anode body; wherein the sealing material is configured to enclose the filler material into the inert anode body between the inner sidewall of the inert anode body and the pin; wherein the sealing material comprises a castable ceramic or cermet including A1 2 03

, SiO 2 , MgO, CaO, Na20, or combinations thereof, wherein the

castable ceramic or castable cermet comprises at least aluminates

and/or silicates, and said at least some of silicates and/or

aluminates of said castable ceramic or castable cermet are

replaced with an anode-matched aggregate and/or off-gas

compatible aggregate specifically tailored to match the inert

anode body; and wherein said anode-matched aggregate and/or off

gas compatible aggregate comprises: aggregates comprising

hematite or magnetite, wherein said inert anode body comprises

hematite or magnetite; aggregates having a composition comprising

at least one major compound of the inert anode body, said major

compound comprising more than 30 wt.% of the composition of the

inert

Page 5a of 38 anode body; or aggregates having a component of an off-gas compatible aggregate selected from NiFe204, NiO, CuAl204, and

CuO.

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Embodiments of the present invention, briefly

summarized above and discussed in greater detail below, can be

understood by reference to the illustrative embodiments of the

invention depicted in the appended drawings. It is to be noted,

however, that the appended drawings illustrate only typical

embodiments of this invention and are therefore not to be

considered limiting of its scope, for the invention may admit to

other equally effective embodiments.

[0031] Figure 1 depicts a block diagram of a generic anode

assembly in accordance an embodiment of the instant disclosure.

[0032] Figure 2 depicts a schematic cut-away side view of an

anode apparatus in accordance with an embodiment of the instant

disclosure.

[0033] Figure 3 depicts a cut-away side view of an embodiment

of an anode apparatus of the instant disclosure.

[0034] Figure 4 depicts a cut-away side view of an embodiment

of an anode apparatus of the instant disclosure.

[0035] Figure 5 depicts a cut-away side view of an embodiment

of an anode apparatus of the instant disclosure.

[0036] Figure 6 depicts a cut-away side view of an embodiment

of an anode apparatus of the instant disclosure.

[0037] Figure 7 depicts a cut-away side view of an embodiment

of an anode apparatus of the instant disclosure.

Page 6a of 38

[0038] Figure 8 depicts a cut-away side view of an embodiment of an anode apparatus of the

instant disclosure.

[0039] Figure 9 depicts a cut-away side view of an embodiment of an anode apparatus of the

instant disclosure.

[0040] Figure 10 depicts a cut-away side view of an embodiment of an anode apparatus of

the instant disclosure.

[0041] Figure 11 depicts a cut-away side view of an embodiment of an anode apparatus of

the instant disclosure.

[0042] Figure 12 depicts a cut-away side view of an embodiment of an anode apparatus of

the instant disclosure.

[0043] Figure 13 depicts a cut-away side view of an embodiment of an anode apparatus of

the instant disclosure.

[0044] Figure 14 depicts a cut-away side view of an embodiment of an anode apparatus of

the instant disclosure.

[0045] Figure 15 depicts a cut-away side view of an embodiment of an anode apparatus of

the instant disclosure.

[0046] To facilitate understanding, identical reference numerals have been used, where

possible, to designate identical elements that are common to the figures. The figures are not

drawn to scale and may be simplified for clarity. It is contemplated that elements and features of

one embodiment may be beneficially incorporated in other embodiments without further

recitation.

DETAILED DESCRIPTION

[0047] Figure 1 depicts a block diagram of a generic anode assembly 10 in accordance an

embodiment of the instant disclosure. In some embodiments of the instant disclosure, the anode

assembly 10 comprises an anode support and an anode apparatus. In some embodiments, the

anode apparatus is mechanically attached to the anode support (e.g. refractory package,

structural support member, combination thereof). In some embodiments, the anode apparatus

comprises: an anode body, a pin, and a sealing material.

[0048] In some embodiments, the anode assembly is a part of an electrolysis cell comprising

a cell structure comprising a cell bottom and a cell sidewall. In some embodiments, the cell

sidewall is configured to perimetrically surround the cell bottom and extend in an upward

direction from the cell bottom to define a control volume. In some embodiments, the control

volume is configured to retain a molten electrolyte bath.

[0049] In some embodiments, the anode body comprises at least one outer sidewall. In some

embodiments, the outer sidewall is configured to define a shape of the anode body and to

perimetrically surround a hole in the anode body. In some embodiments, the hole comprises an

upper opening in a top surface of the anode body and the hole axially extends into the anode

body. In some embodiments, the pin comprises a first end and a second end. In some

embodiments, the first end is connected to a current supply. In some embodiments, the second

end is opposite the first end. In some embodiments, the second end extends downward into the

upper end of the anode body and into the hole of the anode body.

[0050] In some embodiments, the sealing material is configured to cover at least a portion of

at least one of the following: an inner sidewall of the anode body; the top surface of the anode

body; the pin; and the anode support. In some embodiments, the sealing material is configured to cover at least a portion of at least one of the following: an inner sidewall of the anode body; the pin; and a filler material.

[0051] In some embodiments, the sealing material is configured to reduce, prevent, or

eliminate corrosive constituents of the electrolysis process from contacting (and corroding) (1)

the pin and/or (2) the mechanical attachment site of the anode body to the pin. In some

embodiments, the sealing material is configured to be tailored (i.e. matched) to the composition

of the anode body. In some embodiments, the sealing material is configured such that aggregate

present in the sealing material is compositionally consistent with the anode body composition.

In some embodiments, the sealing material is configured to substantially overlap with the

coefficient of thermal expansion of the anode body.

[0052] In some embodiments, the sealing material is inserted into the anode body (between

the inside of the anode body and the pin) as a particulate material. In some embodiments, the

sealing material is inserted into the anode body (between the inside of the anode body and the

pin) as a liquid/slurry applied to the anode body or pin. In some embodiments, when the sealing

material is inserted into/added onto the anode body, it undergoes a chemical and/or thermal cure

in order to form a solid sealing material. In some embodiments, the sealing material is

positioned between the pin and the anode body.

[0053] In some embodiments, a sealing material is utilized around the upper end of the anode

body, surrounding the outer surface of the pin and contacting the anode body (e.g. inner portion

of the hole in the anode body, top surface of the anode body, upper portion of the anode body,

and/or combinations thereof). In some embodiments, the sealing material comprises a cement.

In some embodiments, the sealing material comprises a grout. In some embodiments, the sealing material is configured to prevent corrosive vapors from entering into the inner surface of the anode body, proximal to the portion of the pin that is retained within the anode body.

[0054] In some embodiments cement includes aggregate and a binder or matrix. In some

embodiments, the aggregate is replaced with a sealing material in accordance with the instant

disclosure (e.g. utilizing the commercially available binder and/or matrix). In some

embodiments, the matrix or binder is replaced with a sealing material in accordance with the

instant disclosure (e.g. utilizing the commercially available aggregate). In some embodiments,

the matrix or binder and aggregate is replaced with a sealing material in accordance with the

instant disclosure. Some non-limiting commercial examples of binders, matrices, aggregates,

and/or combinations thereof include: A12 0 3 , SiO2 , MgO,CaO, or the like.

[0055] In some embodiments, the sealing material includes at least one of: water, polymers,

organics, dispersants, and/or diluents in order to promote a flowable sealing material such that

the sealing material is formable/flowable into its desired location (e.g. in the anode assembly

and/or anode body).

[0056] In some embodiments, the sealing material is configured to enclose the conductive

filler into the anode body (i.e. between the inner sidewall of the anode body and the pin). In

some embodiments, the sealing material is configured to provide a mechanical attachment of the

anode body to the pin. In some embodiments, the sealing material is configured to provide

structural support to the anode assembly and/or anode apparatus.

[0057] In some embodiments, the sealing material is cast in place. In some embodiments, an

accelerant is utilized in combination with the sealing material in order to reduce the curing time.

In some embodiments, the sealing material is pre-cast and screwed into the anode body (e.g.

upper portion of the anode body). In some embodiments, the sealing material is sintered into place while/during the sintering of the green form anode body into the final anode body/anode assembly (anode body, pin, and sealing material). In some embodiments, the sealing material is retained above the hole, proximal to the top surface of the upper end of the anode. In some embodiments, sealing material is retained in the hole (i.e. extending between the pin and the inner sidewall of the anode body) and above the top surface of the anode body.

[0058] In some embodiments, above the top surface of the anode body includes extending

along the pin (i.e. portion of the pin that extends out of the anode body). In some embodiments,

above the top surface of the anode body includes extending along the pin and into the anode

support (i.e. portion of the pin that extends into the anode support, where the pin is mechanically

attached). In some embodiments, above the top surface includes extending across the top surface

of the upper portion of the anode body. In some embodiments, above the top surface includes

body (i.e. creating a collar around the upper end of the anode surface).

[0059] As used herein, "anode" means the positive electrode (or terminal) by which current

enters an electrolytic cell. In some embodiments, the anodes (i.e. anode bodies) are constructed

of electrically conductive materials. In some embodiments, the anode comprises an inert anode

(e.g. non-reactive, dimensionally stable, and/or having a dissolution rate (e.g. at the cell

operating parameters) less than that of a corresponding carbon anode).

[0060] As used herein, "anode body" means: the physical structure of the anode (e.g.

including the top, bottom, and sidewall(s)). Some non-limiting examples of anode materials

include: metals, metal alloys, metal oxides, ceramics, cermets, and combinations thereof In

some embodiments, the anode body is oval, cylindrical, rectangular, square, plate-shaped

(generally planar), other geometrical shapes (e.g. triangular, pentagonal, hexagonal, and the like

[0061] As used herein, "anode apparatus" means the anode or positive electrode in the

electrolysis cell. In some embodiments, the anode apparatus includes: the anode body and

anode pin. In some embodiments, the anode apparatus includes the anode body, anode pin, and

filler/sealing materials (e.g. individually, or in combination: conductive filler and/or sealing

material).

[0062] As used herein, "anode assembly" means at least one anode apparatus (anode body,

pin, conductive filler, and/or sealing material) and an anode support, where the at least one

anode apparatus is connected (e.g. mechanically and/or electrically) to the anode support.

[0063] As used herein, "support" means a member that maintains another object(s) in place.

In some embodiments, the support is the structure that retains the anode(s) in place. In one

embodiment, the support facilitates the electrical connection of the electrical bus work to the

anode(s). In one embodiment, the support is constructed of a material that is resistant to attack

from the corrosive bath. For example, the support is constructed of insulating material,

including, for example refractory material. In some embodiments, multiple anodes are

connected (e.g. mechanically and electrically) to the support (e.g. removably attached), which is

adjustable and can be raised, lowered, or otherwise moved in the cell. In some embodiments,

the anode support includes a refractory material (e.g. block or assembly), other bath resistant

materials, rail or beam support members, vertical adjustment components and apparatuses,

and/or electrical bus work.

[0064] As used herein, "electrical bus work" refers to the electrical connectors of one or

more component. For example, the anode, cathode, and/or other cell components can have

electrical bus work to connect the components together. In some embodiments, the electrical bus work includes pin connectors in the anodes, the wiring to connect the anodes and/or cathodes, electrical circuits for (or between) various cell components, and combinations thereof

[0065] As used herein, "sidewall" means: a surface that forms the wall of an object.

[0066] As used herein, "perimetrically surrounding" means: surrounding the outside edge of

a surface. As a non-limiting example, perimetrically surrounding includes different geometries

(e.g. concentrically surrounding, circumscribing) and the like.

[0067] As used herein, "electrolyte bath" (sometimes interchangeably referred to as bath)

refers to a liquefied bath having at least one species of metal to be reduced (e.g. via an

electrolysis process). A non-limiting example of the electrolytic bath composition (in an

aluminum electrolysis cell) includes: NaF-AlF 3, NaF, AlF 3 , CaF 2, MgF 2, LiF, KF, and

combinations thereof --with dissolved alumina.

[0068] As used herein, "molten" means in a flowable form (e.g. liquid) through the

application of heat. As a non-limiting example, the electrolytic bath is in molten form (e.g. at

least about 750°C). As another example, the metal product that forms at the bottom of the cell

(e.g. sometimes called a "metal pad") is in molten form.

[0069] In some embodiments, the molten electrolyte bath/cell operating temperature is: at

least about 750°C; at least about 800°C; at least about 850°C; at least about 900°C; at least

about 950°C; or at least about 975°C. In some embodiments, the molten electrolyte bath/cell

operating temperature is: not greater than about 750°C; not greater than about 800°C; not

greater than about 850°C; not greater than about 900°C; not greater than about 950°C; or not

greater than about 975 °C.

[0070] As used herein, "vapor" means: a substance that is in the form of a gas. In some

embodiments, vapor comprises ambient gas mixed with caustic and/or corrosive exhaust from

the electrolysis process.

[0071] As used herein, "vapor space" refers to the head space in an electrolysis cell, above

the surface of the electrolyte bath.

[0072] As used herein, "interface" refers to a surface regarded as the common boundary of

two bodies, spaces, or phases.

[0073] As used herein, "bath-vapor interface" refers to the surface of bath, which is the

boundary of two phases, the vapor space and the liquid (molten) electrolyte bath.

[0074] As used herein, "metal product" means the product which is produced by electrolysis.

In one embodiment, the metal product forms at the bottom of an electrolysis cell as a metal pad.

Some non-limiting examples of metal products include: aluminum, nickel, magnesium, copper,

zinc, and rare earth metals.

[0075] As used herein, "at least" means greater than or equal to.

[0076] As used herein, "hole" means: an opening into something.

[0077] As used herein, "pin" means: a piece of material used to attach things together. In

some embodiments, the pin is an electrically conductive material. In some embodiments, the pin

is configured to electrically connect the anode body to the electrical buswork in order to provide

current to an electrolysis cell (via the anode). In some embodiments, a first end of the pin is

configured to fit into/be retained within an anode support (e.g. anode support and at least one

anode apparatus is an anode assembly)In some embodiments, the pin is configured to overlap

with the anode body. In some embodiments, the pin is configured to structurally support the

anode body, as it is attached to and suspended from the pin. In some embodiments, the pin is stainless steel, nickel, nickel alloy, Inconel, or a corrosion protected steel. In some embodiments, the pin is configured to extend into the anode body (e.g. into a hole) to a certain depth, in order to provide mechanical support and electrical communication to the anode body.

In some embodiments, the length of the pin is sufficient (long enough) to provide mechanical

support to the anode body and sufficient to (short enough) to prevent corrosion on the pin inside

the hole (i.e. locate the pin above the bath-vapor interface) In some embodiments, the pin is

oval, cylindrical, rectangular, square, plate-shaped (generally planar), other geometrical shapes

(e.g. triangular, pentagonal, hexagonal, and the like).

[0078] As used herein, "attach" means: to connect two or more things together. In some

embodiments, the pin is attached to the anode body. In some embodiments, the pin is

mechanically attached to the anode body by: fastener(s), screw(s), a threaded configuration (e.g.

on pin), a mating threaded configuration (e.g. on inner surface of hole in anode body and on

pin), or the like. In some embodiments, the pin is attached to the anode body via welding (e.g.

resistance welding or other types of welding). In some embodiments, the pin is attached to the

anode body via a direct sinter (i.e. sintering the anode body onto the pin directly).

[0079] As used herein, "electrically conductive material" means: a material that has an

ability to move electricity (or heat) from one place to another.

[0080] As used herein, "filler" means: a material that fills a space or void between two other

objects. In some embodiments, the filler is configured to connect (e.g., electrically connect) the

anode body to the pin. In some embodiments, non-limiting examples of filler include: a

particulate material, a liquid/slurry material, and combinations thereof. In some embodiments,

the filler is incorporated/inserted into the desired location in a flowable form, which then

hardens over time to yield a solid filler material.

[0081] In some embodiments, the filler is a conductive material, also referred to as

conductive filler. In some embodiments, the filler is configured to electrically connect the pin to

the anode body. Non-limiting examples of electrically conductive filler materials include: iron

oxides (hematite, magnetite, wustite), copper, copper alloys, nickel, nickel alloys, precious

metals, (e.g., Pt, Pd, Ag, Au) and combinations thereof.

[0082] As used herein, "sealing material" means: a substance used to close or secure an

object or component (e.g. in order to reduce, prevent, and/or eliminate the transmittal of vapor

or liquid to the object or component). In some embodiments, the filler is configured to seal the

upper portion hole in the anode body from corrosive vapors present in the vapor space. Non

limiting examples of a sealing material include: castable cement, concrete, grout, mortar, and

combinations thereof.

[0083] In some embodiments, the sealing material is a substance/material that includes at

least two components: (1) aggregate and (2) matrix cement (e.g., grout), where the aggregate

includes large and/or fine aggregate sizes. In some embodiments, the sealing material is applied

to an area in order to act as an adhesive, as it is configured to adhere components together upon

hardening.

[0084] As used herein, "castable" means: a substance/material that includes at least two

components: aggregate and cement, where the aggregate includes large and fine aggregate sizes.

In some embodiments, the castable is applied to an area such in order to act as an adhesive, as it

is configured to adhere components together upon hardening.

[0085] As used herein, "grout" means: a castable with matrix and finer aggregate (as

compared to concrete or cement). In some embodiments, the grout includes a viscosity

configured to fill cracks and crevices in the anode assembly and/or anode apparatus. In some embodiments, the grout is configured as a bonding material that hardens in place and is used to bind things together.

[0086] As used herein, "particulate material" means: a material composed of particles. In

some embodiments, the particulate material is electrically conductive. In one embodiment, the

particulate material is copper shot. Other non-limiting examples of particulate materials

include: precious metals (e.g. platinum, palladium, gold, silver, and combinations thereof). As

non-limiting examples, the particulate material includes: metal foam (e.g. Cu foam), large or

small shot (e.g., configured to fit between the pin and the anode body and/or in the anode hole),

paint, and/or powder. Other sizes and shapes of particulate materials are utilizable, provided

they fill the void between the pin and the anode body (or portion below the pin, in the hole of

the anode body) and promote an electrical connection between the anode body and the pin to

provide current to the anode.

[0087] In some embodiments, the sealing material is configured to reduce, prevent, or

eliminate corrosion from the anode apparatus (e.g. pin, anode body, conductive filler, and/or

combinations thereof).

[0088] In some embodiments, the sealing material includes aggregate that is configured as

an anode-matched aggregate. In some embodiments, the sealing material is configured as an off

gas compatible aggregate (e.g., configured to react but not substantially degrade the

effectiveness of the sealing material.

[0089] As used herein, "anode-matched aggregate" (sometimes referred to as off gas

compatible aggregate) means aggregate that has an overlapping performance characteristics as

the anode composition. In some embodiments, anode matched aggregate is aggregate having the

same compositional constituent as the anode body (e.g. hematite, magnetite). In some embodiments, anode matched aggregate is aggregate having a composition that is consistent with at least one major species (or compound) present in the anode (e.g. >30 wt. %). In some embodiments, anode matched aggregate is aggregate having a compound or component of an off-gas compatible aggregate (e.g. NiFe 2 0 4, NiO, CuAl 20 4 , CuO). Some non-limiting examples of aggregating sealing materials include: spinels, magnetite, hematite, copper aluminate, nickel ferrite, or tin oxide, and combinations thereof.

[0090] In some embodiments, the sealing material comprises a castable ceramic or cermet

plug, where the aggregates (or at least a portion thereof) are replaced with an anode-matched

aggregate and/or an off-gas compatible aggregate as the primary seal. As a non-limiting

example, the sealing material comprises a castable ceramic or cermet containing A1 2 0 3 , SiO 2

, MgO, CaO, Na 20, and combinations thereof, where at least some of the silicates and/or

aluminates are replaced with an aggregate specifically tailored/matched to the anode body

and/or pin material, in accordance with the instant disclosure.

[0091] In some embodiments, the aggregate is about 40 wt. % of the sealing material (e.g. as

cured). In some embodiments, the matrix/binder is about 60 wt. % of the sealing material (e.g.

as cured). In some embodiments, the aggregate is from about 5 wt. % to 100 wt. % of the

sealing material. In some embodiments, the binder/matrix is from about 5 wt. % to 100 wt. % of

the sealing material.

[0092] In some embodiments, the percentage and/or quantity of aggregate or binder/matrix is

quantified via SEM (scanning electron microscope) or EDS (energy dispersive spectroscopy),

via viewing/observing a polished cross-section of sealing material. In this embodiment, EDS is

configured to provide the chemical make-up of the cross-section.

[0093] In some embodiments, the filler is conductive filler (e.g. configured to promote

electrical communication between the pin and the anode body).

[0094] In some embodiments, within the hole, where the filler is configured to extend

between the inner sidewall of the anode body and the pin (e.g. beneath the sealing material).

[0095] In some embodiments, the sealing material comprises a thickness of: from 1 mm to

not greater than 50 mm.

[0096] In some embodiments, the sealing material has a thickness of: at least 1 mm; at least 2

mm; at least 3 mm; at least 4 mm; at least 5 mm; at least 6 mm; at least 7mm; at least 8 mm; at

least 9 mm; or at least 10 mm.

[0097] In some embodiments, the sealing material has a thickness of: at least about 5 mm; at

least about 10 mm; at least about 15 mm; at least about 20 mm; at least about 25 mm; at least

about 30 mm; at least about 35 mm; at least about 40 mm; at least about 45 mm; or at least

about 50 mm.

[0098] In some embodiments, the sealing material has a thickness of: not greater than 1 mm;

not greater than 2 mm; not greater than 3 mm; not greater than 4 mm; not greater than 5 mm;

not greater than 6 mm; not greater than 7mm; not greater than 8 mm; not greater than 9 mm; or

not greater than 10 mm.

[0099] In some embodiments, the sealing material has a thickness of: not greater than about

5 mm; not greater than about 10 mm; not greater than about 15 mm; not greater than about 20

mm; not greater than about 25 mm; not greater than about 30 mm; not greater than about 35

mm; not greater than about 40 mm; not greater than about 45 mm; or not greater than about 50

mm.

[00100] In some embodiments, the sealing material has a thickness of at least about 50 mm;

at least about 100 mm; at least about 150 mm; at least about 200 mm; or at least about 250 mm.

In some embodiments, the sealing material has a thickness of: not greater than about 50 mm; not

greater than about 100 mm; not greater than about 150 mm; not greater than about 200 mm; or

not greater than about 250 mm.

[00101] In some embodiments, the sealing material is configured as a coating applied to the

anode pin. In some embodiments, the sealing material is configured as a coating to the inner

surface of the anode body. In some embodiments, the sealing material is configured as a coating

applied to the upper surface (e.g. top end) of the anode body.

[00102] In some embodiments, the sealing material is applied to one or more components of

the anode apparatus and/or anode assembly via washing (e.g., painting) the component directly

with the material.

[00103] In some embodiments, the sealing material is applied to one or more components of

the anode apparatus and/or anode assembly via applying the sealing material to the

component(s) as a slurry/suspension in combination with a binder or liquid.

[00104] In some embodiments, the sealing material is applied to one or more of the anode

apparatus and the pin via applying/directing the aggregate into the desired located (e.g. pouring

powder, particulate, or pellets), followed by adding the matrix, mechanically

agitating/combining, and allowing the sealing material to set/dry.

[00105] In some embodiments, the sealing material is applied to one or more of the anode

apparatus and the pin via spraying.

[00106] In some embodiments, the sealing material is applied to one or more of the anode

apparatus and the pin via gunning.

[00107] In some embodiments, the sealing material is applied to one or more of the anode

apparatus and the pin via slip casting. In some embodiments, the sealing material is applied to

one or more of the anode apparatus and the pin via pressure casting. In some embodiments, the

sealing material is applied to one or more of the anode apparatus and the pin via vacuum

casting. In some embodiments, the sealing material is applied to one or more of the anode

apparatus and the pin via slurry pressing. In some embodiments, the sealing material is applied

to one or more of the anode apparatus and the pin via gel casting. In some embodiments, the

sealing material is applied to one or more of the anode apparatus and the pin via electrophoretic

casting.

[00108] In some embodiments, the anode matched aggregate and/or off-gas compatible

aggregate is present in mixed form with the sealing material, where the aggregate is from at

least 1 vol. % sealing material to not greater than 99.5 vol. % sealing material.

[00109] In some embodiments, the aggregate is present in mixed form with the sealing

material, where the aggregate is from at least 1 vol. % sealing material to not greater than 100

vol. % sealing material.

[00110] As non-limiting examples, the aggregate comprises: at least 1 vol. %; at least 5 vol.

%; at least 10 vol. %; at least 15 vol. %; at least 20 vol. %; at least 25 vol. %; at least 30 vol. %;

at least about 35 vol. %; at least 40 vol. %; at least 45 vol. %; at least 50 vol. %; at least 55 vol.

%; at least 60 vol. %; at least 65 vol. %; at least 70 vol.%; at least 75 vol. %; at least 80 vol. %;

at least 85 vol. %; at least 90 vol. %; or at least 95 vol. %; or at least 99 vol. % of the sealing

material.

[00111] As non-limiting examples, the aggregate comprises: not greater than 1 vol. %; not

greater than 5 vol. %; not greater than 10 vol. %; not greater than 15 vol. %; not greater than 20 vol. %; not greater than 25 vol. %; not greater than 30 vol. %; not greater than about 35 vol. %; not greater than 40 vol. %; not greater than 45 vol. %; not greater than 50 vol. %; not greater than 55 vol. %; not greater than 60 vol. %; not greater than 65 vol. %; not greater than 70 vol.%; not greater than 75 vol. %; not greater than 80 vol. %; not greater than 85 vol. %; not greater than 90 vol. %; or not greater than 95 vol. %; or not greater than 99 vol. % of the sealing material.

[00112] In some embodiments, a mixture of anode matched aggregate and/or off-gas

compatible aggregate and sealing material includes an amount of aggregate which is sufficient

to maintain the ability of the sealing material to adhere components of the anode apparatus (e.g.,

anode body to pin) and/or anode assembly together (e.g., pin to anode support).

[00113] In some embodiments, the sealing material is applied to the anode hole (i.e. between

the pin and the inner surface of the anode body) in a gradient, such that the concentration of

sealing material (with anode-matched aggregate and/or off-gas compatible aggregate) varies in a

radial direction (i.e. differs from a position adjacent to the pin vs. a position adjacent to the

anode sidewall).

[00114] In one embodiment, the gradient is configured such that the concentration of sealing

material is (with anode-matched aggregate and/or off-gas compatible aggregate) higher adjacent

to the pin as compared to adjacent to the inner surface of the anode body.

[00115] In one embodiment, the gradient is configured such that the concentration of sealing

material (with anode-matched aggregate and/or off-gas compatible aggregate) is lower adjacent

to the pin as compared to adjacent to the inner surface of the anode body.

[00116] In some embodiments, the sealing material is applied to the anode hole (i.e. between

the pin and the inner surface of the anode body) in a gradient, such that the concentration of sealing material varies in a lateral direction (i.e. differs from a position adjacent to the opening of the hole/upper surface of the anode body as compared to a position adjacent to the lower end of the anode body).

[00117] In one embodiment, the gradient is configured such that the concentration of sealing

material is higher adjacent to the upper end as compared to adjacent to the lower end of the

anode body.

[00118] In one embodiment, the gradient is configured such that the concentration of sealing

material is lower adjacent to the upper end as compared to adjacent to the lower end of the

anode body.

[00119] In some embodiments, the sealing material is configured with a higher concentration

at a position adjacent to the bath-vapor interface, as compared to either the upper end (in the

vapor phase) or lower end (in the bath) of the anode body.

[00120] In some embodiments, the concentration of sealing material from a position just

below the bath-vapor interface to a position adjacent to the upper end of the anode is higher than

the portion of (anode-matched aggregate and/or off-gas compatible aggregate in the) sealing

material in the submerged portion of the anode body (e.g. submerged below the bath-vapor

interface).

[00121] Figures 2-15 depict schematic cut-away side view of an exemplary anode apparatus in

accordance with some embodiments of the instant disclosure. Figure 2 depicts an anode

apparatus wherein the sealing material 50 covers a portion of the pin 12 in vapor space 24, the

opening 32 and an entire top surface of the anode body 30. Figure 3 depicts an anode apparatus

wherein the sealing material 50 covers an entirety of the pin 12 in vapor space 24, the opening

32 and a portion of the top surface of the anode body 30. Figure 4 depicts an anode apparatus wherein the sealing material 50 covers a portion of the pin 12 in vapor space 24, the opening 32, and a portion of the top surface of the anode body 30. Figure 5 depicts an anode apparatus wherein the sealing material 50 covers an entirety of the pin 12 above the top surface of the anode body 30 (i.e. within the vapor space 24 and refractory portion 18), the opening 32, and a portion of the top surface of the anode body 30.

[00122] Figure 6 depicts an anode apparatus wherein the sealing material 50 covers an

entirety of the pin 12 in vapor space 24, the opening 32 and an entire top surface of the anode

body 30. In Figure 6, the sealing material 50 extends beyond a peripheral edge of the top

surface of the anode body and covers a portion of the sidewall 40 of the anode body 30. Figure 7

depicts an anode apparatus wherein the sealing material 50 covers a portion of the pin 12 in

vapor space 24, the opening 32, and an entire top surface of the anode body 30. In Figure 7, the

sealing material 50 extends beyond a peripheral edge of the top surface of the anode body and

covers a portion of the sidewall 40 of the anode body 30.

[00123] Figure 8 depicts an anode apparatus wherein the sealing material 50 covers an

entirety of the pin 12 in vapor space 24. The sealing material 50 covers opening 32 and an

entire top surface of the anode body 30. The sealing material 50 extends beyond a peripheral

edge of the top surface of the anode body and covers a portion of the sidewall 40 of the anode

body 30. Sealing material 50 is also disposed between the vapor space 24 and the refractory 18

to prevent corrosive chemicals from corroding exposed portions of the pin 12 (i.e. not covered

by sealing material 50).

[00124] Figure 9 depicts an anode apparatus wherein the sealing material 50 covers a portion

of the pin 12 in vapor space 24, the opening 32, and an entire top surface of the anode body 30.

The sealing material 50 extends beyond a peripheral edge of the top surface of the anode body and covers a portion of the sidewall 40 of the anode body 30. A portion of the pin 12 in the vapor phase 24 is not covered by sealing material 50. Sealing material 50 is also disposed between the vapor space 24 and the refractory 18 to prevent corrosive chemicals from corroding exposed portions of the pin 12 in the refractory 18.

[00125] Figure 10 depicts an anode apparatus wherein the sealing material 50 covers an

entire top surface of the anode body 30. The sealing material 50 does not extend beyond a

peripheral edge of the top surface of the anode body to cover a portion of the sidewall 40 of the

anode body 30. Sealing material 50 is also disposed between the vapor space 24 and the

refractory 18 to prevent corrosive chemicals from corroding exposed portions of the pin 12 (i.e.

not covered by sealing material 50).

[00126] Figure 11 depicts an anode apparatus wherein the sealing material 50 covers a portion

The sealing material 50 extends beyond a peripheral edge of the top surface of the anode body

and covers a portion of the sidewall 40 of the anode body 30. The sealing material extends

down the sidewall 40 of the anode body 30 proximate to the interface 22.

[00127] Figure 12 depicts an anode apparatus wherein the sealing material 50 covers a portion

of the pin 12 in vapor space 24, the opening 32 and an entire top surface of the anode body 30.

[00128] Figure 13 depict an anode apparatus wherein the sealing material 50 covers a portion

The sealing material is also disposed within the hole 34 to cover a portion of the pin 12 within

the anode body 30. The sealing material 50 covers a portion of the pin 12 within the anode

body 30 that is above the interface 22.

[00129] Figure 14 depicts an anode apparatus wherein the sealing material 50 is disposed

within the hole 34 to cover a portion of the pin 12 within the anode body 30. The sealing

material 50 covers a portion of the pin 12 within the anode body 30 that is above the interface

22.

[00130] Figure 15 depicts an anode apparatus wherein the sealing material 50 is disposed

22. A filler material is disposed within the hole 34 below the sealing material 50.

[00131] Reference will now be made in detail to prophetic examples, which (in combination

with the accompanying drawings and previous descriptions thereof) at least partially assist in

illustrating various pertinent embodiments of the present invention.

[00132] Example: Prophetic Anode Manufacture:

[00133] Non-limiting examples of producing the anode body include: press sintering, fuse

casting, and casting, which is disclosed in corresponding US Patent 7,235,161, which contents

are incorporated by reference herein by their entirety.

[00134] Once the anode body is formed, the pin and filler materials, if being used, are

incorporated into the anode body. For example, if a filler (e.g. conductive filler) is utilized, the

pin is placed in the hole of the anode body and filler (e.g. in the form of particulate material) is

inserted into the void between the pin and the inner surface of the hole in the anode body. Then

the sealing material (i.e., in order to provide a mechanical attachment and/or seal the pin and/or

filler material into the hole in the anode body), is added to the upper end of the anode body. In

some embodiments, the sealing material is configured to extend at least partially into the hole in

the anode body. In some embodiments, the sealing material is configured to sit on top of the anode body, proximal to the upper end of the hole, and surrounding the pin as it extends upward from the anode body. In some embodiments, the sealing material is placed on top of the anode body in a position surrounding the pin.

[00135] In some embodiments, the sealing material is configured to extend a portion of the

way into the hole at the upper end of the anode. In some embodiments, the sealing material is

configured to cover the top portion of the anode body. In some embodiments, the sealing

material is configured to contact at least a portion of the outer perimetrical sidewall of the anode

body. In some embodiments, the sealing material is configured to contact the pin, the inner

portion of the anode body (hole), the upper portion/top surface of the anode body, and the upper

portion of at least a portion of the outside perimetrical wall of the anode body.

[00136] While various embodiments of the present invention have been described in detail, it

is apparent that modifications and adaptations of those embodiments will occur to those skilled

in the art. However, it is to be expressly understood that such modifications and adaptations are

within the spirit and scope of the present invention.

[00137] Prophetic Comparative Example:

[00138] Two anode assemblies (AAl = prior art and AA2 = an embodiment in accordance

with the instant disclosure) are made with: the same anode body dimensions and composition in

accordance with that set out in disclosures of US Patent Nos. 7,507,322 and 7,235,161; the same

pin material (copper or copper alloy); and different sealing materials.

[00139] In AAl the first instance (prior art), the sealing material is in accordance with the

disclosure of US 7,169,270. In the second instance (instant disclosure), the sealing material has

5 wt. % to 100 wt. % the sealing material is a castable ceramic or cermet containing A1 2 0 3 ,

SiO2 , MgO, CaO, Na 20, and combinations thereof, where at least some of the silicate and/or aluminate aggregates in the sealing material (e.g. castable ceramic) are replaced with a magnetite aggregate (e.g. anode-matched/anode compatible aggregate), configured with comparable sizing as the aggregate appropriate sizing as the aggregate in the prior art run.

[00140] Both anode assemblies are configured as the embodiment shown in Figure 2. Both

anode assemblies were incorporated into an aluminum electrolysis cell and operated as

electrodes (anodes) extending across the bath-vapor interface for a sufficient length of time in

order to evaluate whether any reactions occur as a result of the interaction of the reactive species

present in the vapor space of the cell with the sealing material and/or components thereof.

[00141] Anode assemblies are pulled out of the cell and evaluated in order to evaluate and/or

quantify corrosion on the various anode apparatus components (e.g. sealing material). It will be

found that the sealing material of AA2, i.e. sealing material with aggregate tailored (i.e.

matched) to the anode body, performed better (exhibits less corrosion) than the prior art sealing

material. Also, it will be found that the pin of AA2 performed better (exhibits less corrosion)

than the pin of AAl (the prior art anode apparatus).

[00142] Without being bound by a particular mechanism or theory, it is believed that during

cell operating conditions (i.e. at elevated temperature and in a corrosive environment in the

vapor space, which contains reactive fluoride gas, oxygen gas, and/or other reactive vapor

species), the silica (e.g. SiO2 present as aggregate in the sealing material) creates pockets of

reactive silicates available to interact with the reactive species present in the vapor space.

[00143] Without being bound by a particular mechanism or theory, it is believed that the

reactive silicates in the aggregates of the sealing material (i.e. AA1) will react with fluoride gas

present in the vapor space of the cell, in turn creating silicon tetrafluoride, which is in turn

corrosive to the pin. Without being bound by a particular mechanism or theory, it is believed that as the reactive silicon fluoride species further interacts/reacts with the pin, pockets or holes are created in the sealing material (i.e. reducing the mechanical strength/structural support of the sealing material, and yielding pores/holes where the reactive species can further penetrate into and react with the sealing material, or other components of the anode apparatus. Without being bound by a particular mechanism or theory, as the silicon fluoride species react with the pin materials, initiation sites of corrosion occur on the pin and the structural integrity of the anode apparatus and/or the electrical efficiency of this component are further reduced).

[00144] Without being bound by a particular mechanism or theory, it is believed that during

species), the magnetite aggregate (e.g. SiO 2 and/or A1 2 0 3 replacement in the sealing material)

creates pockets of aggregate tailored to not undergo significant reactions with the reactive

species (and thus, will not form pores in the sealing material and/or further attribute to pin

corrosion).

[00145] Without being bound by a particular mechanism or theory, it is believed that the

corrosive to the pin.

[00146] Various ones of the inventive aspects noted hereinabove may be combined to yield

inert anode apparatuses having a pin which provides a mechanical and electrical connection to

the anode body, where the pin extends down into the hole of the anode body and is positioned

such that the lower end of the pin is located above the vapor-bath interface.

[00147] These and other aspects, advantages, and novel features of the invention are set forth

in part in the description that follows and will become apparent to those skilled in the art upon

examination of the following description and figures, or may be learned by practicing the

invention.

Reference Numbers

Anode Assembly 10

Pin 12

First end 14

Second end 16

Anode support 18

Current supply 20

Bath-vapor interface 22

Vapor space 24

Bath 26

Anode apparatus 28

Anode body 30

Upper opening 32

Anode inner sidewall (defining the hole) 34

Upper end of anode 36

Lower end of anode 38

Anode outer sidewall 40

Conductive filler 42

Particulate (conductive filler) material 44

Liquid/Slurry (conductive filler) material 46

Top surface of anode 48

Sealing material 50

Aggregate 52 (large and/or small fines, e.g., aggregate particulate, powder)

Matrix/Binder material 54

Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

1. An inert anode assembly, comprising:

an anode support; and

an inert anode apparatus mechanically attached to the anode support, wherein the inert anode apparatus comprises:

(a) an inert anode body comprising at least one outer sidewall, wherein the outer sidewall is configured to define a shape of the inert anode body, and to perimetrically surround a hole in the inert anode body, wherein the hole comprises an upper opening in a top surface of the inert anode body and wherein the hole axially extends into the inert anode body;

(b) a pin comprising:

a. a first end connected to a current supply, and

b. a second end opposite the first end, wherein the second end extends downward into the upper end of the inert anode body and into the hole of the inert anode body;

(c) a filler material inside the hole and configured to electrically connect the anode body to the pin, wherein the filler material is retained in the hole between an inner sidewall of the inert anode body and the pin; and

(d) a sealing material configured to reduce, prevent and/or eliminate corrosion of the inert anode apparatus, the sealing material comprising an aggregate selected from anode-matched aggregate and/or off-gas compatible aggregate, and a matrix, wherein the sealing material is bonded to the top surface of the anode body and configured to cover the top surface of the anode body and at least a portion of at least one of the following:

(1) the inner sidewall of the inert anode body;

(2) the filler material;

(3) the pin; and

(4) the anode support;

and

wherein at least a portion of the sealing material is retained above the top surface of the inert anode body;

wherein the sealing material is configured to enclose the filler material into the inert anode body between the inner sidewall of the inert anode body and the pin;

wherein the sealing material comprises a castable ceramic or cermet including A1 2 0 3 , SiO 2 , MgO, CaO, Na20, or combinations thereof, wherein the castable ceramic or castable cermet comprises at least aluminates and/or silicates, and said at least some of silicates and/or aluminates of said castable ceramic or castable cermet are replaced with an anode-matched aggregate and/or off-gas compatible aggregate specifically tailored to match the inert anode body; and

wherein said anode-matched aggregate and/or off-gas compatible aggregate comprises:

aggregates comprising hematite or magnetite, wherein said inert anode body comprises hematite or magnetite;

aggregates having a composition comprising at least one major compound of the inert anode body, said major compound comprising more than 30 wt.% of the composition of the inert anode body; or

aggregates having a component of an off-gas compatible aggregate selected from NiFe20 4 , NiO, CuAl204, and CuO.

2. The inert anode assembly of claim 1, wherein the sealing material further comprises at least one of: water, a dispersant, or a diluent, to promote a flowable sealing material such that the flowable sealing material flows and covers said at least a portion of the inert anode apparatus.

3. The inert anode assembly of claim 1 or 2, wherein the aggregate is specifically tailored to not undergo significant reactions with the anode body and/or the pin.

4. The inert anode assembly of any one of claims 1 to 3, wherein, the first end of the pin is configured to be retained within the anode support.

5. The inert anode assembly of any one of claims 1 to 4, wherein the sealing material is cast in place.

6. The inert anode assembly of any one of claims 1 to 5, wherein a part of the sealing material is pre-cast and screwed into the inert anode body.

7. The inert anode assembly of any one of claims 1 to 6, wherein a part of the sealing material is retained in the hole.

8. The inert anode assembly of any one of claims 1 to 7, wherein above the top surface of the inert anode body includes extending along the pin.

9. The inert anode assembly of any one of claims 1 to 8, wherein above the top surface of the inert anode body includes extending along the pin and into the anode support.

10. The inert anode assembly of any one of claims 1 to 9, wherein above the top surface includes extending across the top surface of the upper portion of the inert anode body.

11. The inert anode assembly of any one of claims 1 to 9, wherein above the top surface includes extending across the top surface and extending down around the outer sidewall of the inert anode body.

12. The inert anode assembly of any one of claims 1 to 11, wherein a part of the sealing material is applied to the anode hole between the pin and the inner surface of the inert anode body in a gradient, such that a concentration of said aggregate of the sealing material varies in a radial direction.

13. The inert anode assembly of any one of claims 1 to 11, wherein a part of the sealing material is applied to the anode hole between the pin and the inner surface of the inert anode body in a gradient, such that the concentration of said aggregate varies in a lateral direction.

14. The inert anode assembly of claim 13, wherein the sealing material is configured with a higher concentration of said aggregate at a position adjacent to a bath-vapor interface, as compared to either the upper end in a vapor phase or the lower end in a bath of the inert anode body.

15. The inert anode assembly of claim 13, wherein the concentration of said aggregate of the sealing material from a position just below a bath-vapor interface to a position adjacent to the upper end of the anode is higher than a portion of sealing material in a submerged portion of the inert anode body.

16. The inert anode assembly as claimed in any one of claims 1 to 1, wherein the inert anode body comprises metals, metal alloys, metal oxides, ceramics, cermets or combinations thereof.

17. An electrolysis cell, comprising:

a cell structure comprising a cell bottom and a cell sidewall, wherein the cell sidewall is configured to perimetrically surround the cell bottom and extend in an upward direction from the cell bottom to define a control volume, wherein the control volume is configured to retain a molten electrolyte bath; and

an inert anode assembly configured to direct current into the molten electrolyte bath, wherein the inert anode assembly comprises: an anode support; and an inert anode apparatus mechanically attached to the anode support, wherein the inert anode apparatus comprises:

(a) an inert anode body comprising at least one outer sidewall, wherein the outer sidewall is configured to define the anode shape and to perimetrically surround a hole in the inert anode body, wherein the hole comprises an upper opening in a top surface of the inert anode body and wherein the hole axially extends into the inert anode body;

(b) an pin comprising: a first end connected to a current supply, and a second end opposite the first end, wherein the second end is configured to extend down into the upper end of the inert anode body and into the hole of the inert anode body;

(d) a sealing material configured to reduce, prevent and/or eliminate corrosion of the inert anode apparatus, the sealing material, and comprising an aggregate selected from anode-matched aggregate and/or off-gas compatible aggregate, and a matrix, the sealing material being bonded to the top surface of the anode body and configured to cover the top surface of the anode body and at least a portion of at least one of the following: an inner sidewall of the inert anode body; the filler material; the pin; and the anode support; and

wherein said anode-matched aggregate and/or off-gas compatible aggregate comprises: aggregates comprising hematite or magnetite, wherein said inert anode body comprises hematite or magnetite; aggregates having a composition comprising at least one major compound of the inert anode body, said major compound comprising more than 30 wt.% of the composition of the inert anode body; or aggregates having a component of an off-gas compatible aggregate selected from NiFe20 4 , NiO, CuAl204, and CuO.

18. The inert anode assembly of claim 17, wherein above the top surface includes extending across the top surface and extending down around the outer sidewall of the inert anode body.

19. The inert anode assembly of claim 17 or 18, wherein the aggregate is specifically tailored to not undergo significant reactions with the anode body and/or the pin.