HK1158369B - Three-dimensional secondary battery with auxiliary electrode - Google Patents

Description

Three-dimensional secondary battery with auxiliary electrode

Technical Field

The present invention relates to three-dimensional secondary battery cells and secondary batteries and methods of making such devices and systems containing such cells and batteries.

Background

Secondary batteries are a type of rechargeable battery in which ions move between an anode and a cathode through an electrolyte. Secondary batteries include lithium ion, sodium ion, potassium ion batteries, and lithium batteries, as well as other types of batteries. Secondary batteries are often formed from a number of battery cells that are grouped together to form a battery. Each cell of the secondary battery includes an electrolyte and at least one cathode and at least one anode. When the cells are grouped together to form a battery, the cathode and anode of each cell may be electrically coupled to obtain a desired battery capacity.

In a secondary battery cell, both the anode and cathode include materials into which carrier ions are inserted and from which they are extracted. The process by which carrier ions move into the anode or cathode is called intercalation. The reverse process of carrier ions moving out of the anode or cathode is called precipitation. During cell discharge, carrier ions are extracted from the anode and inserted into the cathode. When charging a battery cell, the exact opposite process occurs: carrier ions are extracted from the cathode and inserted into the anode.

Lithium ion batteries are a common type of secondary battery in which the carrier ions are lithium ions that move between a cathode and an anode through an electrolyte. The advantages and difficulties of lithium ion cells are exemplary of the advantages and difficulties of other secondary cells; the following examples of lithium ion battery cells are illustrative and not limiting. In a lithium ion battery cell, lithium ions move from the anode to the cathode during discharge and from the cathode to the anode during charge. Lithium ion batteries are a very desirable energy source because of their high energy density, high power and long shelf life. Lithium ion batteries are commonly used in consumer electronics and are one of the most common forms of batteries for portable electronics today because they have a high energy-to-weight ratio, no memory effect, and slow charge loss when not in use. Because of these advantages, lithium ion batteries have become increasingly popular in a wide range of applications including automotive, military, and aerospace applications.

Fig. 1 is a cross-section of a prior art lithium ion battery. The battery 15 has a cathode current collector 10 with a cathode 11 assembled on top of the cathode current collector 10. The cathode 11 is covered by a separator 12, on which separator 12 an assembly of an anode current collector 13 and an anode 14 is arranged. The separator 12 is filled with an electrolyte capable of transporting ions between the anode and the cathode. Current collectors 10, 13 serve to collect and connect the electrical energy generated by cell 15 to other cells and external devices so that the external devices are powered and carry the electrical energy to the battery during recharging.

For most existing secondary batteries, there is a significant drop in total capacity after the first charge. For example, in a standard lithium ion battery, the total charge capacity loss after the first charge-discharge cycle is about 5-15%. In addition, most existing secondary batteries lose a portion of their capacity with each subsequent charge-discharge cycle. For example, in a standard lithium ion battery, the total charge capacity loss after each subsequent charge-discharge cycle is about 0.1%.

Three-dimensional energy cells and batteries can produce higher energy storage and recovery per unit geometric area than conventional two-dimensional (or planar) devices. Three-dimensional secondary batteries additionally have the decisive advantage of providing a higher energy recovery rate for a specific amount of energy stored than a planar counterpart by means of, for example, minimizing or reducing the transport distance for electron and ion transfer between the anode and the cathode. These devices are more amenable to miniaturization and are suitable for applications where the available geometric area of the device is limited and where energy density requirements are higher than those obtainable with planar devices. A three-dimensional secondary battery cell may be one in which any one (or more) of the anode, cathode, and separator is itself non-planar, and the actual surface area of such non-planar component is greater than twice its geometric surface area. In some cases, the separation between the two height planes in the third dimension should be at least greater than the number of periods in the x-y plane divided by the square root of 2. For example, for a 1cm x 1cm sample, the geometric surface area is 1cm². However, if the sample is not flat but has a depression in the depth direction with a depth greater than the square root of 1 divided by 2 (or 0.707cm), its actual surface area may be greater than 2cm²。

U.S. patent No.5,304,433 describes the use of a reference electrode in a lead acid battery to monitor the voltage of the negative electrode and estimate the state of charge. In this patent, the reference electrode measures the voltage at a particular point of the cell and this value may not be representative of the entire cell. Furthermore, the voltage signal is used as a direct indication of the state of charge. This approach is problematic when the battery is in use, especially for high dynamic curves, because the state of charge (SOC) and voltage relationships are not clear.

U.S. patent No.7,373,264 describes a method of estimating SOC and state of health (SOH) of a battery in dynamic operation by determining initial values of a set of parameters, coefficients and derivatives based on a linear functional relationship and analyzing these values by least squares regression. Alternatively, the method of US 7,321,220 may be used to estimate SOC and SOH. These approaches are effective for some battery systems, but are problematic in other situations. For example, these methods are ineffective if the cell voltage versus SOC relationship changes over time. In addition, these methods do not perform well when the cell voltage is relatively independent of the state of charge, as is the case with batteries based on lithium ion phosphate positive electrodes and graphite negative electrodes.

Disclosure of Invention

The present invention is directed to three-dimensional secondary battery cells, batteries, and systems containing the same, as well as methods of making the same. The three-dimensional secondary battery of the present invention includes an electrolyte, a cathode, an anode, and an auxiliary electrode, wherein at least one of the electrodes is non-planar. The cathode, the anode, and the auxiliary electrode each have a surface in contact with the electrolyte. The anode and cathode are galvanically coupled, which means that the carrier ions of the cell can be transferred from the anode to the cathode and from the cathode to the anode via the electrolyte. The auxiliary electrode is electrolytically and electrically coupled to at least one of the anode or the cathode. Electrically coupled means connected directly or indirectly through wires, traces, or other connecting elements. The average distance between the auxiliary electrode and the coupled cathode or the coupled anode is between about 10-1000 microns, preferably 20-500 microns, more preferably 100-500 microns. The average distance represents the average of the shortest paths for ion transfer from each point on the surface of the coupled cathode or anode to each point on the surface of the auxiliary electrode.

Brief Description of Drawings

FIG. 1 is a cross-section of a prior art lithium ion battery; and

fig. 2 is a diagram of a secondary battery cell of the present invention;

fig. 3 is a diagram of a system of the present invention including a secondary battery cell of the present invention;

fig. 4 is a diagram of a system of the present invention including a secondary battery cell of the present invention;

FIG. 5 is a graph of cathodic potential versus time for a lithium auxiliary electrode in accordance with an example of the present invention;

FIG. 6 is a graph of anode potential versus time for a lithium auxiliary electrode according to an example of the present invention; and

fig. 7 is a graph of cell voltage and anode potential versus time for a lithium auxiliary electrode according to an example of the invention.

Detailed description of the invention

The inventors of the present invention have found that a three-dimensional secondary battery cell comprising an auxiliary electrode can be manufactured, thereby alleviating the problems associated with capacity loss after the first and subsequent charge/discharge cycles and allowing for enhanced control during the charge/discharge cycles of the battery cell or cell.

The present invention is directed to a three-dimensional secondary battery cell comprising an electrolyte, a cathode, an anode, and an auxiliary electrode, wherein at least one of the cathode, anode, and auxiliary electrode is non-planar. In one embodiment, both the cathode and the anode are non-planar. The cathode, the anode, and the auxiliary electrode each have a surface in contact with the electrolyte. The anode and cathode are galvanically coupled, which means that the carrier ions of the cell can be transferred from the anode to the cathode and from the cathode to the anode via the electrolyte. The auxiliary electrode is electrolytically and electrically coupled to at least one of the anode or the cathode. Electrically coupled means connected directly or indirectly through wires, traces, or other connecting elements. The average distance between the auxiliary electrode and the coupled cathode or the coupled anode is between about 10-1000 microns, preferably 20-500 microns, more preferably 100-500 microns. The average distance represents the average of the shortest paths for ion transfer from each point on the surface of the coupled cathode or anode to each point on the surface of the auxiliary electrode.

The auxiliary electrode may be composed of various materials such as an alkali metal foil and an insertion material. For lithium ion batteries, lithium metal foil is particularly useful as an auxiliary electrode, whereas intercalation materials such as lithium titanate, graphite, and silicon used as a negative electrode and positive electrode materials such as lithium cobalt oxide, lithium manganese oxide, lithium nickel cobalt oxide, and lithium ion phosphate may be used as auxiliary electrodes. The auxiliary electrode may be in the form of a metal foil, a coated metal foil or a coated mesh.

The auxiliary electrode (third electrode) of the present invention may be used to increase the capacity of the energy storage device, improve the rate of device charging and/or discharging control and/or monitor the device's performance over time. The prior art auxiliary electrode used as a reference electrode in a two-dimensional cell is ineffective in passing current due to the large resistance across the single electrode of the two-dimensional structure. The difference between the auxiliary electrode of the three-dimensional secondary battery cell and the conventional reference electrode is that the auxiliary electrode is brought close to almost all portions of the cathode and/or anode due to the non-planar configuration of the cathode, anode and/or auxiliary electrode, whereby the auxiliary electrode can pass a large amount of current. In the present invention, the auxiliary electrode is close to the anode and/or cathode of the three-dimensional secondary battery cell, which provides a short transport distance and allows carrier ions to reach almost all parts of the cathode and/or anode. The short transmission distance results in a much lower ohmic resistance between the electrodes compared to conventional planar cell configurations. This allows a large amount of current to pass and the potential to be measured more accurately.

The introduction of auxiliary electrodes in three-dimensional secondary battery cells is of great significance in terms of battery monitoring and maintenance. For example, the auxiliary electrode may serve as a reference electrode and be used for accurate measurement of state of charge (SOC) and state of health measurement (SOH).

The auxiliary electrode in the three-dimensional secondary battery cell of the present invention provides a good measurement of the average voltage of the entire negative or positive electrode, avoiding the problem of single-point reference. Furthermore, the voltage signals from the electrodes can be adapted in real time to the model giving the SOC and/or SOH estimation. The use of the third electrode of the invention provides good measurements when the cell voltage versus SOC varies over time or when the cell voltage is relatively independent of the state of charge (e.g. batteries based on a lithium ion phosphate positive electrode and a graphite negative electrode).

When the auxiliary electrode has a large electrochemical capacity, it can be used to charge/discharge the positive electrode or the negative electrode in a cell balancing mechanism. This ability solves the problem of uneven self-discharge between the positive and negative electrodes, since they are both charged with the third electrode.

Fig. 2 is a diagram of an exemplary embodiment of a secondary battery cell of the present invention. The cell includes at least one cathode 20, at least one anode 22, and an auxiliary electrode 24. Although the auxiliary electrode 24 is illustrated as a single-piece structure, it may also comprise multiple electrode elements or portions. The cathode 20 may include a cathode current collector 21. Anode 22 may include an anode current collector 23. If the cell includes multiple cathodes 20, the cathodes 20 may be electrically coupled to one another. If the cell contains multiple anodes 22, the anodes 22 may be electrically coupled to each other. The cell contains a separator 25 positioned between the cathode 20 and the anode 22. The cell also includes a separator 29 between the auxiliary electrode and the cathode 20 or anode 22.

The separator 29 between the auxiliary electrode 24 and the cathode 20 or anode 22 may be of the same material as the separator 25 or a different material may also be used. Separator 25 comprises an electrolyte capable of transporting the carrier ions of the cell. In the embodiment of fig. 2, auxiliary electrode 24 is electrically coupled to cathode 20. The electrical coupling between auxiliary electrode 24 and cathode 20 may include means 27 for sensing a control current or voltage and storing information about the current or voltage.

In one embodiment, the auxiliary electrode is electrically coupled to the cathode, wherein the cathode comprises a cathode material that is atmospherically unstable in its carrier ion-inserted form. The material being unstable to the atmosphere in its carrier ion inserted form being material and/or intercalatedA material in which carrier ions react with components in the air. Examples of cathode materials that may be unstable in their carrier ion-inserted form include titanium sulfide (e.g., titanium disulfide, TiS)₂) Molybdenum sulfide (e.g., molybdenum disulfide), and vanadium oxide (e.g., V)₂O₅). For example, lithium intercalated into titanium sulfide reacts with oxygen and water vapor in air. In another embodiment, the auxiliary electrode acts as an auxiliary cathode. A cathode combined with an auxiliary cathode may achieve better performance than a cathode alone. One example of a cathode and an auxiliary cathode with improved performance is LiMn₂O₄And LiNi_0.8Co_0.15Al_0.05O₂They are electrically coupled together as cathodes. By electrically coupling the two cathodes together, better battery cycle life and performance can be achieved.

In another embodiment of the three-dimensional secondary battery cell of the present invention, the auxiliary electrode may be electrically coupled to the anode. In embodiments where the auxiliary electrode is electrically coupled to the anode, the auxiliary electrode may serve as an auxiliary anode. An anode in combination with an auxiliary anode may achieve better performance than an anode alone. Alternatively, the auxiliary electrode may be electrically coupled to both the cathode and the anode. In another embodiment, the anode comprises an anode material, wherein the anode material is atmospherically unstable in its carrier ion-inserted form. Examples of anode materials that are atmospherically unstable in their carrier ion insertion form include silicon, germanium, carbon, tin, aluminum, mixtures of transition metals and silicon, and lithium titanate.

In another embodiment, the anode and cathode comprise materials that are atmospherically unstable in their carrier ion-inserted form. Because the carrier ions of the cell may not be introduced to either the cathode or the anode prior to assembly of the cell, cells in which both the anode and cathode comprise materials that are atmospherically unstable in their carrier ion-inserted form have been prohibitively dangerous and/or expensive to manufacture. For example, titanium sulfide/graphite cells are not suitable for use as the cathode/anode of conventional lithium ion cells, as neither titanium sulfide nor graphite can the cells be made in the form of lithium oxide. However, the use of an auxiliary lithium electrode makes it possible to utilize cathode materials like titanium sulfide, molybdenum sulfide and vanadium oxide, the anode of which is like silicon, germanium, carbon, tin, aluminum, mixtures of transition metals and silicon and lithium titanate. After assembling and sealing the cell with all three electrodes, the auxiliary electrode can be used to introduce carrier ions like lithium ions to the anode and/or cathode.

The batteries and cells of the invention may comprise aqueous or non-aqueous electrolytes.

As shown in fig. 3, one embodiment of the present invention relates to a system including a secondary battery cell 31 positioned as described above with respect to the auxiliary electrode, a sensor 38, and a controller 39. Sensor 38 senses the voltage of at least one of cathode 30 or anode 32 relative to auxiliary electrode 34. Sensor 38 is electrically coupled to cathode 30 or anode 32 at a location where a voltage is sensed, and to auxiliary electrode 34. In fig. 3, sensor 38 is illustrated as being electrically coupled to both cathode 30 and anode 32. However, the present invention also includes embodiments in which sensor 38 is coupled only to cathode 30 or anode 32. Controller 39 is electrically coupled to sensor 38 and controller 39 is capable of controlling the voltage or current in the load/charging circuit between cathode 30 and anode 32 based on the sensed voltage. The load/charge circuit between cathode 30 and anode 32 is a circuit that contains a load driven by the current produced by the cell as it discharges, or a circuit through which electrical energy is used to recharge the cell. Cathode 30 and anode 32 are electrolytically coupled through the electrolyte in separator 35. Auxiliary electrode 34 is electrolytically coupled to at least one of cathode 30 or anode 32 through the electrolyte in separator 35.

In fig. 3, the auxiliary electrode 34 is electrically coupled to the cathode 30. However, the present invention includes embodiments in which auxiliary electrode 34 is electrically coupled to anode 32 and embodiments in which auxiliary electrode 34 is electrically coupled to both cathode 30 and anode 32. The electrical coupling between auxiliary electrode 34 and cathode 30 or anode 32 may include means 37 for sensing or controlling the current or voltage and storing information about the current or voltage. A component 37 electrically coupled between auxiliary electrode 34 and cathode 32 or anode 30 may be electrically coupled to sensor 38 and controller 39.

As shown in FIG. 4, an embodiment of the system of the present invention may include a storage unit 40 coupled to the sensor, wherein the storage unit 40 stores data regarding the sensed voltage. The storage unit 40 may be coupled to the controller 39, and the controller 39 may control the voltage or current in the load/charge circuit based on the data stored in the storage unit 40 and based on the voltage detected by the sensor 38. Using the memory unit 40, the auxiliary electrode of the present invention may be used to monitor the charging and/or discharging process of the secondary battery cell by allowing for memory device failure mode identification, identification of battery capacity and/or life changes, programmable notification of battery end-of-life, and the like.

The auxiliary electrode 34 of the present invention may be used to control the charge and/or discharge rate of the battery cell. This may be achieved by making the auxiliary electrode of a reference material that can be used to tune and/or stop the charge and/or discharge rate. For most existing rechargeable energy storage devices, discharge is allowed to continue until the potential difference between the anode and cathode reaches a lower limit based on the battery chemistry. However, in some cases it may be advantageous to stop the discharge at an anode or cathode potential relative to a fixed reference value rather than at a potential relative to each other. For example, in the case of a silicon anode as part of a lithium ion battery, the lifetime of the silicon anode is reduced and the silicon anode is no longer stable in the case of a full discharge. Ideally, the discharge should stop when the silicon anode reaches a voltage of 0.9V with respect to lithium. In a conventional lithium ion battery, the anode voltage is controlled indirectly by the voltage difference between the anode and the cathode in the battery cell, and the battery cell voltage. However, the use of an auxiliary lithium electrode electrically and electrolytically coupled to at least one of the cathode or the anode allows for direct monitoring of the anode and the cathode, and thus the potential of the anode can be directly controlled and maintained above 0.9V relative to the auxiliary electrode. Other potential auxiliary electrode materials that may be used are lithium alloys, carbonaceous materials, lithium metal oxides, and lithium metal phosphides.

In another embodiment of the present invention, the auxiliary electrode 34 may serve as a means for rapidly recharging the secondary battery cell. For most existing secondary battery cells, the charge rate of the device is set by charging the anode or the cathode or both at a constant current that is relatively low to ensure that the overpotential of charge carriers returning from the cathode to the anode is not so high that device degradation occurs. For example, in a standard lithium ion battery, if the 4.3V drive voltage of the cathode with respect to the lithium reference is exceeded, undesirable side effects may occur on the cathode. Also, the anode voltage must be kept above a certain value. In a standard lithium ion cell, where the anode must remain above 0V with respect to lithium, i.e. lithium deposition occurs on the anode, to ensure that these negative effects on the cathode and anode do not occur, existing secondary cells are charged with a battery cut-off voltage of 4.2V, so that the 4.3V cathode voltage threshold cannot be exceeded and the 0.1V anode threshold voltage cannot be passed. However, with the auxiliary electrode, the electrode is actually driven at a selected voltage to maximize current transfer and reduce charging time. Preferably, the increased current used to charge the battery cell of the present invention should correspond to a rate of at least C/100 relative to the capacitance (C) of the electrode being charged. However, it more preferably corresponds to at least a C/50 charge rate, most preferably at least a C/20 charge rate.

Fig. 3 also shows how the auxiliary electrode 34 acts as a reference electrode to stop the discharge when the voltage of the anode 32 and/or cathode 30 exceeds a prescribed limit relative to the auxiliary electrode 34. One embodiment of the invention may be implemented by sensing the voltage of cathode 30 or anode 32 relative to auxiliary electrode 34 with sensor 38. Controller 39 may isolate the battery cell from the circuitry being powered when a predetermined voltage limit is exceeded.

Controller 39 of fig. 4 may cause auxiliary electrode 34 to replenish at least one of the cathode or anode depending on the voltage sensed by sensor 38. Alternatively, the controller 34 may cause the auxiliary electrode 34 to replenish at least one of the cathode or the anode according to data stored in the storage unit 40 or according to both the voltage sensed by the sensor 38 and the data stored in the storage unit 40.

To supplement cathode 30 or anode 32, an electric current may be applied between auxiliary electrode 34 and cathode 30 or anode 32. For example, for a lithium ion secondary cell, the use of lithium foil as an auxiliary electrode, and the application of current between the lithium foil and the anode can replenish the capacity loss in the first cycle and/or subsequent cycles of the cell. In an embodiment of the secondary battery cell of the present invention, the battery cell has been cycled and the cathode or anode has been supplemented by an auxiliary electrode.

The present invention includes a method of making a supplemental secondary battery cell comprising: obtaining a secondary battery cell as described herein; periodically operating the anode and the cathode of the battery cell; and at least one of the coupled cathode or anode is replenished with carrier ions from the auxiliary electrode. After replenishment, the auxiliary electrode may be removed from the secondary battery cell. The auxiliary electrode may be removed to reduce the weight or volume of the battery cell or to improve the reliability or safety of the battery cell or a battery in which the battery cell is integrated.

Supplementing the cathode or anode and removing the auxiliary electrode before the secondary battery cell is finally packaged can improve the energy density of the battery cell. After the first charge and/or discharge cycle, the lost energy capacity can be replenished by auxiliary electrode material diffusing into the anode and/or cathode (a cell cycle is the charging or discharging of a cell). Diffusion of the auxiliary electrode material may be achieved by applying a voltage across the auxiliary electrode and the cathode and/or anode alone to drive material transfer between the auxiliary electrode and the anode and/or cathode or by other transport phenomena that drive the transfer of auxiliary electrode material to the anode and/or cathode.

If the auxiliary electrode is not removed from the cell, replenishment can be done after final packaging and the auxiliary electrode will remain in the final cell. If auxiliary electrodes are left in the finally packaged battery cell and the corresponding battery, the battery cell may achieve capacity replenishment to supplement capacity fade that occurs during cycling of the battery cell.

The auxiliary electrode of the present invention can be formed by placing an electrode made of a desired material in the inactive area of the cell unit but still allowing it to be electrolytically coupled to the anode and/or cathode through the separator. Alternatively, the auxiliary electrode may be formed by depositing the desired auxiliary electrode material using techniques such as electrochemical deposition, electroless deposition, electrophoretic deposition, vacuum assisted filling, stencil assisted filling, and the like.

The three-dimensional secondary battery cell of the present invention can be incorporated into a three-dimensional secondary battery. Three-Dimensional secondary batteries can be made according to the methods of the present invention or by employing methods well known in the art, for example, see Three-Dimensional Battery architecture (Three-Dimensional Battery structure) by Long et al, chemical reviews, 2004, 104, 4463-; the university of Electrochimica by Wang and Cao, 51, 2006, 4865-; and Nishizawa et al journal of the electrochemical society, 1923-1927, 1997; shemble et al 5^thAdvanced Batteries and Accumulators (fifth generation Advanced Batteries and Accumulators), ABA-2004.

The three-dimensional secondary battery of the present invention may include a plurality of three-dimensional secondary battery cells as described herein, wherein cathodes of the plurality of battery cells are electrically coupled, anodes of the plurality of battery cells are electrically coupled, and auxiliary electrodes of the plurality of battery cells are also electrically coupled.

The following examples further illustrate the invention. These examples are intended only to illustrate the invention and are not to be construed in a limiting sense.

Examples of the invention

Example 1: three-dimensional battery cell with lithium foil auxiliary electrode as reference electrode

A three-dimensional cell is constructed from a 1cm by 1cm silicon wafer containing two sets of walls, walls 120 microns high and 100 microns apart. One set of walls was used as the cathode and coated with a slurry containing lithium nickel cobalt aluminum oxide, carbon black and polyvinylidene. The other set of walls acts as an anode. The anode and cathode walls are separated by a porous separator. A third electrode comprising a lithium metal foil is positioned over the wall and separated from the wall by a polyolefin separator (Celgard 2325). The lithium foil is electrolytically coupled to all of the anode and cathode walls by placing the lithium foil on top of the three-dimensional structure. The entire assembly is placed in a metallized plastic capsule, with electrolyte added, and the capsule sealed. The cathode was cycled against the lithium foil. Fig. 5 shows the potential 50 of the cathode relative to the auxiliary electrode. The anode was then cycled for the first time against the lithium foil. Fig. 6 shows the potential 60 of the anode relative to the auxiliary electrode. Finally, the anode was cycled against the cathode while monitoring the cell voltage and the voltage of the anode against the lithium foil auxiliary electrode. Fig. 7 shows a graph of one full charge/rest/discharge cycle, wherein the cell voltage 70 and the anode voltage, 71 are given relative to the auxiliary electrode.

While the invention has been described with reference to the presently preferred embodiments, it will be understood that various modifications may be made without departing from the scope of the invention.

Claims (24)

1. A three-dimensional secondary battery cell comprising:

an electrolyte, a cathode, an anode and an auxiliary electrode;

wherein the electrolyte is in contact with surfaces of the cathode, the anode, and the auxiliary electrode;

the anode is electrically decoupled from the cathode; and

the auxiliary electrode is electrically and electrolytically coupled to the cathode and/or the anode, and an average distance between the auxiliary electrode and a coupled cathode or a coupled anode is about 10 to 1000 microns, wherein at least one of the cathode, the anode and the auxiliary electrode is non-planar,

wherein the average distance between the surface of the auxiliary electrode and the coupled cathode or the coupled anode is an average of the shortest paths for ion transfer from each point on the surface of the coupled cathode or anode to each point on the surface of the auxiliary electrode.

2. The three-dimensional secondary battery cell of claim 1, wherein the cathode and the anode are non-planar.

3. The three-dimensional secondary battery cell of claim 1, wherein an average distance between the auxiliary electrode and the coupled cathode or the coupled anode is between about 100 microns and about 500 microns.

4. The three-dimensional secondary battery cell of claim 1, wherein the auxiliary electrode is electrically and electrolytically coupled to the cathode.

5. The three-dimensional secondary battery cell of claim 4, wherein the cathode comprises a cathode material, and the cathode material is atmospherically unstable in its carrier ion-inserted form.

6. The three-dimensional secondary battery cell of claim 5, wherein the cathode material comprises titanium sulfide, molybdenum sulfide, or vanadium oxide.

7. The three-dimensional secondary battery cell according to claim 4, wherein the auxiliary electrode functions as an auxiliary cathode.

8. The three-dimensional secondary battery cell of claim 1, wherein the auxiliary electrode is electrically and electrolytically coupled to the anode.

9. The three-dimensional secondary battery cell of claim 8, wherein the anode comprises an anode material and the anode material is atmospherically unstable in its carrier ion-inserted form.

10. The three-dimensional secondary battery cell of claim 9, wherein the anode material comprises silicon, germanium, carbon, tin, aluminum, a mixture of transition metals and silicon, or lithium titanate.

11. The three-dimensional secondary battery cell of claim 8, wherein the auxiliary electrode functions as an auxiliary anode.

12. The three-dimensional secondary battery cell of claim 1, wherein the anode comprises an anode material, the cathode comprises a cathode material, and the anode material and the cathode material are atmospherically unstable in their carrier ion-inserted form.

13. The three-dimensional secondary battery cell of claim 1, wherein the auxiliary electrode comprises a plurality of electrode elements.

14. The three-dimensional secondary battery cell of claim 1, wherein the electrolyte is a non-aqueous electrolyte.

15. The three-dimensional secondary battery cell of claim 1, wherein the battery cell has been cycled and the cathode or anode has been replenished by the auxiliary electrode.

16. A three-dimensional secondary battery comprising the three-dimensional secondary battery cell according to claim 1.

17. A three-dimensional secondary battery comprising a plurality of the three-dimensional secondary battery cells of claim 1, wherein cathodes of the plurality of battery cells are electrically coupled, anodes of the plurality of battery cells are electrically coupled, and auxiliary electrodes of the plurality of battery cells are electrically coupled.

18. A system comprising the three-dimensional secondary battery cell of claim 1;

a sensor for sensing a voltage of the cathode and/or the anode relative to the auxiliary electrode, wherein the sensor is electrically coupled to the cathode and/or the anode at which the sensed voltage is located and to the auxiliary electrode; and

a controller electrically coupled to the sensor, wherein the controller controls a voltage or current in a load or charging circuit between the cathode and anode according to the sensed voltage.

19. The system of claim 18, further comprising a storage unit coupled to the sensor, wherein the storage unit stores data about the sensed voltage.

20. The system of claim 19, wherein the storage unit is coupled to the controller, and the controller controls a voltage or current in the load/charge circuit according to the data stored in the storage unit.

21. The system of claim 18, wherein the controller causes the auxiliary electrode to replenish at least one of the cathode or anode in accordance with the sensed voltage.

22. The system of claim 19, wherein the controller causes the auxiliary electrode to replenish at least one of the cathode or anode in accordance with the data stored in the memory unit.

23. A method of making a supplemented three-dimensional secondary battery cell, comprising:

obtaining a three-dimensional secondary battery cell of claim 1;

cycling the anode and the cathode of the battery cell; and

the coupled cathode or the coupled anode is replenished with carrier ions from the auxiliary electrode.

24. The method of claim 23, further comprising removing the auxiliary electrode from the three-dimensional secondary battery cell.