US20200024153A1

US20200024153A1 - Precursors of cathode materials for a rechargeable lithium ion battery

Info

Publication number: US20200024153A1
Application number: US16/488,717
Authority: US
Inventors: Dae-Hyun Kim; Jens Paulsen; JinDoo OH; Maxime Blangero
Original assignee: Umicore NV SA; Umicore Korea Ltd
Current assignee: Umicore NV SA; Umicore Korea Ltd
Priority date: 2017-03-08
Filing date: 2018-02-07
Publication date: 2020-01-23
Also published as: FI3592706T3; EP3592706B1; KR20190122847A; WO2018162165A1; JP6920455B2; KR20190122846A; CN110475752B; KR20190122257A; EP3592706A1; CN110734098A; HUE063153T2; US11189832B2; KR102327114B1; KR102327120B1; US20200017370A1; JP6940568B2; JP2021054717A; JP2020109048A; CN110844943A; JP2020510975A

Abstract

A method for manufacturing a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure, comprising the steps of: —providing an first aqueous solution comprising a source of Co, —providing a second aqueous solution comprising Na2CO3, —mixing both solutions in a precipitation reactor at a temperature above 70° C., thereby precipitating a cobalt based hydroxide carbonate compound whilst evacuating from the reactor any CO2 formed by the precipitation reaction, wherein the residence time of the compound in the reactor is between 1 and 4 hours, and—recovering the cobalt based hydroxide carbonate compound. The cobalt based hydroxide carbonate compound is used as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries.

Description

TECHNICAL FIELD AND BACKGROUND

This invention relates to a powderous cobalt based compound, applicable as a precursor of a cathode material in a rechargeable lithium ion battery, and to a process to use this precursor to prepare a cathode material for rechargeable lithium ion batteries. More particularly, the precursor compound is a cobalt based hydroxide carbonate based compound which is prepared by a precipitation process using sodium carbonate. In an embodiment, the precursor compound is additionally doped with elements such as Al, Mg, Mn, Ni etc. and, preferably the compound has a spherical morphology, which provides benefits for improved electrochemical performance and higher energy density.
Lithium cobalt oxide (LiCoO₂; referred to as LCO hereafter)—doped or un-doped—has been used as a cathode material in the rechargeable batteries of most commercial portable electronic applications, such as a mobile phone, tablet PC, laptop computer, and digital camera, due to its high energy density and good cycle life. LCO has a hexagonal α-NaFeO₂type structure (space group of R-3 m), where layers of lithium ions are located between slabs of CoO₆octahedron. Since the demand for smaller and lighter batteries which have a high energy density and good electrochemical properties has increased, lots of R&D groups are working on developing or improving cathode materials, especially LCO.
There are several ways to increase the volumetric energy density of a lithium ion battery such as applying a thinner current collector and separator, and using cathode and anode materials which have a higher packing density. The packing density of a cathode material mainly depends on two components:

- first, the particle size distribution (referred to as PSD hereafter) of LCO is directly linked to the volumetric density because it determines how close particles can be packed in a limited volume. Generally, a higher D50 value (being the particle size of the median particle in a normal distribution) tends to enable a higher packing density. Furthermore, the D100 (or D99) value should be as low as possible, because big particles result in bad electrode coating quality, and damage to the current collector. The span, which is the value of (D90-D10)/D50), is a useful criterion to identify how similar in size the particles are, and defines the relative particle size of big particles compared to the D50. The smaller the span, the less large particle issues are expected, even if the D50 is large to obtain a large density.
- second, the porosity in a single particle should be as low as possible to get a maximum density of a single particle.

LCO is synthesized using a lithium (Li) precursor (generally, Li₂CO₃) and a cobalt (Co) precursor (typically, Co₃O₄). There are two possibilities to obtain a target D50 value of LCO. One is to adjust the synthesis conditions such as sintering temperature, sintering time, and Li to Co ratio. For a sufficient high Li to Co ratio and sintering temperature, inter-particle sintering occurs and the D50 increases significantly. This allows to use non-shaped cobalt precursors, as their size is determined by the sintering conditions. A draw-back of this approach is that high sintering temperatures are required, which increases process costs and/or the obtained LCO has a high Li to Co stoichiometry, which is bad for electrochemical performance. This dilemma was discussed in detail in W02009-003573.
An alternative approach is to use pre-shaped cobalt precursors, such as spherical Co₃O₄, as disclosed in US2015/0221945. The word “shaped” here refers to a precursor that already resembles the desired shape of the final LCO. This relaxes the sintering requirements. This approach is preferred because it is expected that the particle size of LCO is irregular—having a wider span—when a non-shaped cobalt precursor is used. Also, high temperature or high Li to Co ratio is mandatory to shape LCO from non-shaped cobalt precursor, requiring high energy consumption or additional heat treatment steps to get a stoichiometric LCO. The way to get the preferred morphology of LCO is to start a synthesis from shaped cobalt precursors that have a high D50 and narrow span. Having a high density and low porosity is a benefit as it further enhances the packaging density of the final LCO and reduces the sintering efforts. Shaped cobalt precursor should also have enough mechanical hardness not to be broken during processing, such as blending with the lithium precursor.
A cathode material is one of the most critical components which determine the electrochemical properties of lithium ion batteries. One way to increase the energy density of a lithium ion battery is to increase its working voltage by applying a higher charge voltage. However, as the state of charge increases by increasing the charge voltage, less lithium ions remain in the crystal structure, resulting in a thermodynamically unstable CoO₂. Thus, as a result of reactions of the delithiated cathode material with the electrolyte, cobalt can slowly be dissolved in the electrolyte at high voltage, which is referred to as cobalt dissolution, resulting in the failure of the battery. There have been tremendous efforts to reduce cobalt dissolution by means of doping LCO. Preferably, the dopant is already present and well distributed in the cobalt precursor before sintering, such as in CN102891312 A, CN105731551 A and CN102583585 B. This is because it is difficult to obtain good doping in large particles by a solid state approach where a shaped cobalt precursor is blended with the dopant. Full diffusion of dopant into the shaped particles of LCO requires a long sintering time or very high sintering temperatures. This especially applies for a synthesis process if the particle size is big, e.g. >10 μm, where the dopant is added during blending of lithium and cobalt precursors.
Cobalt precursors for LCO can be prepared by a precipitation process. For example, a solution having a certain concentration of a CoSO₄and a solution having a certain concentration of NaOH are mixed in a reactor under controlled pH, where an impeller is rotating with a certain RPM. Consequently, solid cobalt hydroxide (Co(OH)₂) will be precipitated, which can be a cobalt source of LCO. However, there is a drawback when using Co(OH)₂in that it is difficult to achieve a large D50 hydroxide because of certain particle growth limitations.
Compared to a Co(OH)₂precipitation process, a CoCO₃precipitation allows more easily to obtain large, spherical and dense cobalt precursors. For the precipitation, cobalt salts can be chosen from CoSO₄, CoCl₂, Co(NO₃)₂or other water soluble cobalt salts, while bases can be selected from Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, NH₄HCO₃or other soluble carbonate or bicarbonate. Na₂CO₃, NaHCO₃and NH₄HCO₃are the three most widely used precipitation agents for CoCO₃.
Nowadays CoCO₃is typically produced through a co-precipitation of a bicarbonate solution with a cobalt salt solution. If CoSO₄is chosen as cobalt salt, a typical reaction equation is:
CoSO₄+2AHCO₃→CoCO₃+A₂SO₄+H₂CO₃, with A=H or NH₄ (EQ 1)
If, for example, CoCl₂is used as cobalt salt the reaction equation would accordingly be:
CoCl₂+2AHCO₃→CoCO₃+2ACl+H₂CO₃, with A=Na, K, or NH₄ (EQ 2)
Additionally there will be side reactions as H₂CO₃dissociates to H₂O+CO₂or by NH₃evolution for A=NH₄. A drawback of the bicarbonate process according to EQ1 and 2 above is that only 50% of the available —CO₃is utilized in the product. 50% of the —CO₃remains in solution or evaporates as CO₂.
In a typical NH₄HCO₃process, when using CoSO₄, the basic reaction is:
CoSO₄+2NH₄HCO₃→CoCO₃+(NH₄)₂SO₄+CO₂+H₂O (EQ 3)
During the precipitation, CO₂is continuously released from the reactor and (NH₄)₂SO₄is generated as a by-product. It can be calculated that 1kg CoCO₃product needs 1.329 kg of NH₄HCO₃. Sulfur (S) and Nitrogen (N) are the main impurities in the obtained CoCO₃product in this process. Because the (NH₄)₂SO₄cannot be released to the environment, the waste water needs to be treated to remove—preferably to recycle—the ammonia. These ammonia recycling installations are expensive and increase the capital investment significantly, as well as the operating cost for the waste treatment, in particular by the higher need of energy.
In a process using NaHCO₃, when using CoSO₄the reaction is:
CoSO₄+2NaHCO₃→CoCO₃+Na₂SO₄+CO₂+H₂O (EQ 4)
It can be calculated that 1kg CoCO₃product needs 1.413 kg of NaHCO₃. Compared with the NH₄HCO₃process, there is no need to install an ammonia recovery system. However, the throughput of the NaHCO₃process is an issue. Compared to the high solubility of NH₄HCO₃(216 g/L at 20° C.), the solubility of NaHCO₃is relative low (96 g/L at 20° C.). Therefore, higher flow rates of less concentrated NaHCO₃are needed for the precipitation, which results in a relative low throughput of the CoCO₃production. On the other hand, because the dissolution of NaHCO₃is very slow, an independent dissolution/storage facility is necessary for mass production.
Another obvious approach is to use a carbonate for the precipitation. A typical reaction equation—if MSO₄is used as salt—is:
MSO₄+A₂CO₃→MCO₃+A₂SO₄, with A=Na, K or NH₄ (EQ 5)
However, WO2016-055911 teaches that—if M is Ni—Mn—Co—and A=Na or K—a MCO₃precipitates that has a high content of alkali impurities.
This invention aims to provide an improved cobalt based precursor compound for a cathode material, and a manufacturing method to obtain a low impurity content in the final cathode material, which improves the electrochemical stability and increases the energy density of the cathode material, with a cheaper process cost.

SUMMARY

View from a first aspect, the invention can provide the use of a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries. The compound may have the general formula [Co_1-aA_a]₂(OH)₂CO₃, A being either one or more of Ni, Mn, Al, Zr, Ti and Mg, with a0.05. In an embodiment A is Al or Mg, with 0.002≤a≤0.020, and Al or Mg is homogeneously doped in the compound. The compound may have an XRD pattern where the peak ratio P has a value <1, with P=P1/P2, P1 being the maximum peak intensity at 32˜33 degree, and P2 being the maximum peak intensity at 34˜35 degree. P might also be <0.8 or even <0.2 to yield a superior compound. The same values for P can also be reached if the compound is part of a mixture comprising also cobalt carbonate. The cobalt carbonate may have a rhombohedral structure. The compound in the previous embodiments may further comprise Na as an impurity of up to 0.3wt %. Also, the compound may have a particle size distribution with D50 between 15 and 25μm or between 20 and 25 μm, and a span <0.80. Another PSD related characteristic may be that D99/D50 <2. Furthermore the cobalt based hydroxide carbonate compound may have a spherical morphology and a tap density >1.8 g/cm³.
Viewed from a second aspect, the invention can provide a method for manufacturing the cobalt based hydroxide carbonate compound of the first aspect of the invention, comprising the steps of:

- providing an first aqueous solution comprising a source of Co,
- providing a second aqueous solution comprising Na₂CO₃,
- mixing both solutions in a precipitation reactor at a temperature above 70° C., thereby precipitating a cobalt based hydroxide carbonate compound whilst evacuating from the reactor any CO₂formed by the precipitation reaction, wherein the residence time of the compound in the reactor is between 1 and 4 hours, and
- recovering the cobalt based hydroxide carbonate compound. In a particular embodiment, the step of mixing both solutions can be performed in an open precipitation reactor to facilitate the evacuation of CO₂, and in another embodiment the open reactor can be exposed to the air. The residence time can further be limited to between 1 and 3 hours and the temperature to between 80 and 95° C.: taking into account water evaporation, the maximum reaction temperature may be limited to 95° C. In the method embodiments, the second aqueous solution may consist of either:
- a solution of at least 2N Na₂CO₃, or
- a solution consisting of between 0.5 and 3 mol/L of Na₂CO₃and between 1 and 6 mol/L NaOH, wherein the Na content in the Na₂CO₃is as high or higher than twice the Na content in the NaOH. In an embodiment, the solution consists of between 1.5 and 2.5 mol/L of Na₂CO₃and between 3 and 5 mol/L NaOH, wherein the Na content in the Na₂CO₃is as high or higher than twice the Na content in the NaOH. In an embodiment the solution consists of >50 vol % of a 2 mol/L Na₂CO₃solution and <50 vol % of a 4 mol/L NaOH solution. It may also be that the first aqueous solution further comprises a source of either one or more of Ni, Mn, Al, Mg and Ti. In a further embodiment, the solution comprising a source of Co comprises CoSO₄, and further comprises either one or more of MgSO₄, Al₂(SO₄)₃, NiSO₄and MnSO₄, wherein either one or more of Mg,Al, Ni and Mn are present in a molar ratio versus the Co content of between 0.2 and 5 mol %. Another way to add the dopant A may be that during the step of mixing both solutions a nanometric powder consisting of either one or more of TiO₂, MgO and Al₂O₃is added. In a particular method embodiment the step of recovering the cobalt based hydroxide carbonate compound comprises the substep of transferring the compound to a settlement reactor coupled to the precipitation reactor, and whereafter from the settlement reactor the settled compound is recirculated to the precipitation reactor.

The invention can also provide a method to manufacture a lithiated cobalt based oxide, comprising the steps of any one of the previous method embodiments, and subsequently comprising the steps of:

- mixing the cobalt based hydroxide carbonate compound with a source of Li, and
- sintering the mixture at a temperature above 950° C. in an oxygen containing atmosphere.

In this method, the precipitated cobalt based hydroxide carbonate compound may comprise Na as an impurity between 0.1 and 0.3 wt %, and wherein either:

- during the step of mixing the cobalt based hydroxide carbonate compound with a source of Li, or
- during the step of sintering the mixture;

a sulfate compound is added, whereby the molar quantity of SO₄is equal to or higher than the molar content of Na, and subsequently comprising the step of washing the lithiated cobalt based oxide with water, and drying the lithiated cobalt based oxide. Here, the sulfate compound may be either one of Li₂SO₄, NaHSO₄, CoSO₄and Na₂S₂O₈.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1: Typical result of floating test

FIG. 2: Schematic illustration of Na₂CO₃based co-precipitation set-up

FIG. 3: The XRD patterns of cobalt hydroxide carbonate based cobalt precursors

FIG. 4: Relation between the proportion of Co₂(OH)₂CO₃phase and amount of sodium impurity

FIGS. 5a & b: EDS mapping of EX3-P-3

DETAILED DESCRIPTION

The current invention discloses a cobalt compound useful as cobalt precursor of a cathode material for a rechargeable lithium ion battery. More specifically, this precursor is a cobalt hydroxy (or hydroxide) carbonate based compound. In the drawings and the following detailed description, preferred embodiments are described in detail to enable practice of the invention. Although the invention is described with reference to these specific embodiments, it will be understood that the invention is not limited to these preferred embodiments. To the contrary, the invention includes numerous alternatives, modifications and equivalents, as will become apparent from considering the detailed description and the accompanying figures.
This invention provides:
1) a cobalt precursor compound for a cathode material in rechargeable lithium ion batteries,
2) a method to produce this cobalt compound and
3) a method to produce the cathode material having a low impurity level, which is a benefit for improved electrochemical performance.
In the area of precursors for cathodes for rechargeable lithium batteries, precipitation is widely applied. Quite generally ammonia is added as chelating agent (for example to prepare M(OH)₂) or as part of the precursor salts (for example ammonium bicarbonate in the case of CoCO₃). Ammonia containing solutions are not stable, and especially at higher temperatures and higher pH they decompose rapidly and NH₃gas evolves. Therefore it is standard practice to (1) use closed reactors and (2) avoid high temperatures to avoid a contamination of the air in the plant by ammonia.
It is assumed that under these process conditions a CoCO₃precursor can also be precipitated through a Na₂CO₃process and when using CoSO₄the reaction theoretically is:
CoSO₄+Na₂CO₃→CoCO₃↓+Na₂SO₄ (EQ 6)
It can be calculated that 1 kg CoCO₃product only needs 0.892 kg of Na₂CO₃, which is much less than when using NaHCO₃and NH₄HCO₃. Since Na₂CO₃is cheaper than NaHCO₃and NH₄HCO₃, the Na₂CO₃precipitation process is more attractive from a cost point of view. The main problem for a Na₂CO₃process is generally the high sodium impurity in the final obtained MCO₃product. In a typical Na₂CO₃process, sodium reaches several thousand ppm, sometimes even 10000 ppm in the final obtained CoCO₃precursor. High impurities levels will result in a poor electrochemical performance of the obtained LCO, especially a low reversible capacity. New strategies need to be applied to solve the sodium impurity problem in CoCO₃precursor products. Besides impurities in general, a particular issue is that in a standard precipitation, no high quality precipitate is achieved. Typically the precipitate of a CoSO₄+Na₂CO₃precipitation has a poor morphology and a very low density.
The invention discloses that a cobalt based hydroxide carbonate compound can be produced by using a Na₂CO₃precipitation process that is performed at high temperature under agitation, and ensuring that any CO₂that is formed is evacuated from the reactor mixture.
The invention combines the following aspects:
1) Based on a Na₂CO₃precipitation process, which is cost-efficient, a spherical dense cobalt compound which has narrow span can be prepared: the median particle size (D50) of the precipitated cobalt hydroxide carbonate can be easily above 20 μm with a span below 0.8. Due to the feature of a spherical dense cobalt compound which has a narrow span, the cathode material (LCO) can have also have a higher density and narrower span.
2) A dopant (Ni, Mn, Nb, Al, Mg, Ti, Zr, and etc.) can be homogeneously distributed in the crystal structure of the cobalt precursor compound with atomic scale distribution, since the dopant is added during the precipitation process. Surprisingly, doping of 3-valent aluminum into the structure of the cobalt compound is possible. Additionally, contrary to other processes, doping of Mg is possible as well. Besides of atomic scale distribution, nano-particle doping can be applied as well (for example for TiO₂). As aluminum suppresses the structural changes at high voltage, the influence of cobalt dissolution on the electrochemical properties of the final lithiated cobalt based oxide can be mitigated. Doping of manganese in a cobalt precursor can stabilize the crystal structure of LCO resulting in the improved cycleability as well as the power performance of LCO. Nickel doping can increase the capacity of LCO.
3) The sodium impurity can be generally suppressed in the cobalt hydroxide carbonate compound. However, in some conditions, a Na impurity remains after the precipitation, which can be removed by an intermediate washing step after addition of sulfur or chlorine compounds, followed by a drying step.
Surprisingly, in these conditions a precipitate of high quality can be achieved, related to the surprising discovery that the high quality precipitate is not a cobalt based carbonate but rather a cobalt hydroxide carbonate. In order to precipitate a cobalt hydroxide carbonate from a Na₂CO₃base feed—as will be described later in detail—CO₂is evaporated continuously from the solution. CO₂only evaporates if the temperature during precipitation is sufficiently high and when an appropriate evacuation of CO₂is foreseen, such as by working with an open reactor. If the CO₂evaporation rate is insufficient cobalt carbonate precipitates instead of the desired cobalt hydroxide carbonate, and high quality precursors are not achieved.
In general, for the precipitation reaction, a flow comprising Na₂CO₃, a flow comprising CoSO₄or CoCl₂, and another flow of dopant source are fed into a reactor under normal to strong agitation. Typically, the agitation is achieved by a rotating impeller or circulating flows. The precipitation reaction can be a batch process or a continuous process where the overflow is circulated back into the reactor. Under normal agitation, the precipitation process is mainly controlled by the following parameters:

- Temperature
- Residence time
- pH
- Metal concentration
- CO_3/Co (or base/acid) molar ratio

After precipitation, the obtained cobalt bearing precursor is separated from the liquid by a suitable separation technique such as filtering, then washed by deionized water. Washing with deionized water can remove a fraction of the sodium impurity from the obtained cobalt baring precursor, but still a quite high amount of impurities remain even after washing with large amounts of deionized water. The obtained cobalt bearing precursor—which still contains some water—is dried in a drying oven at elevated temperature.
It is observed that depending on the above mentioned precipitation process parameters, the precipitated material comprises a cobalt hydroxide carbonate that may be represented by the general formula Co₂(OH)₂CO₃, according to the reaction:
2CoSO₄+2Na₂CO₃+H₂O→Co₂(OH)₂CO₃↓+2Na₂SO₄+CO₂↑ (EQ 7)
Besides this cobalt hydroxide carbonate, the precipitated material can also contain CoCO₃, according to the theoretical reaction mentioned before (EQ 6). Nucleation and growth of the precipitated particles is related to the precipitation reaction kinetics. Since large spherical particles having a narrow span can be obtained in this process, it implies that during precipitation, existing particles grow and no or only a small number of new particles are created. Thus the main process is the precipitation of Co₂(OH)₂CO₃onto existing Co₂(OH)₂CO₃particles, resulting in the desired particle growth. The inventors speculate that the precipitation reaction happens in two steps. CoCO₃could precipitate as an intermediate, metastable compound, which then reacts with liquid, and by an ion exchange process results in the hydroxide carbonate compound, according to the following reaction schemes:
2CoCO₃+2H₂O→Co₂(OH)₂CO₃+H₂CO₃ (EQ 8)
H₂CO₃→H₂O+CO₂↑ (EQ 9)
The inventors assume that the rate limiting step is the ion exchange reaction (EQ 8). Thus if the temperature is too low or the CO₂is not effectively evacuated, the ion exchange kinetics are negatively influenced and residual CoCO₃remains. If the residual CoCO₃exceeds 50% by weight, the sodium impurity level increases severely and the preferred morphology is not obtained anymore. Only if the cobalt hydroxide carbonate phase dominates, a precursor of high quality is obtained. The reaction in (EQ 7) is promoted by a high temperature during the precipitation process, preferably in a well agitated open-type reactor, so that generated CO₂can easily be removed from the system. It has thus been found that if the base is Na₂CO₃, the precipitation needs to be performed at a temperature of at least 70° C., preferably at around 90° C., preferably in an open reactor, to allow the evolution of CO₂.
During the precipitation, the flow of base comprises a solution of Na₂CO₃. Alternatively, the base can be a mixture of Na₂CO₃and NaOH, where up to 50% of the Na present in Na₂CO₃can be replaced by NaOH. A 50% molar solution (Na₂CO₃+2NaOH) does not require the evolution of CO₂, following the reaction:
2CoSO₄+Na₂CO₃+2NaOH→Co₂(OH)₂CO₃+2Na₂SO₄ (EQ 10)
As the NaOH content in the base flow increases less CO₂needs to evaporate and the precipitation temperature can be lowered.
In order to achieve a complete precipitation of cobalt, it is recommended that the ratio of base to acid is larger than 1. If it is too low, unreacted cobalt remains in the solution. For example, if 100% Na₂CO₃is used, the molar ratio of CO₃to Co should be at least 1. If a 50/50% Na₂CO₃/NaOH mixture is used, the ratio of (CO₃+2OH) to Co should be at least 1. The Na₂CO₃content in the base should not be below 50% (CO₃>2OH). In this case, too much NaOH is present and some of the precipitate will be Co(OH)₂which is undesired.
The base and acid concentration may be sufficient high to achieve a low nucleation rate and a high reactor throughput. If Na₂CO₃is used, a typical concentration is at least 2N, which corresponds to 1 mol Na₂CO₃/L, preferably it is at least 3N and most preferably at least 4N. The acid solution is typically at least 2N, corresponding to 1 mol CoSO₄/L, more preferably at least 3N and most preferably at least 4N.
The residence time is the time needed to fill the reactor: it is the reactor volume divided by the sum of the feed flow rates. The residence time should be sufficiently high to allow particles to grow into the desired shape. It should not be too high because this would cause a low reactor throughput and more carbonate type precursor formed instead of the desired hydroxy-carbonate.
Homogeneously distributed dopants may play an important role in a cathode material. For example, aluminum significantly suppresses changes in crystal structure of a cathode material when charged to a high voltage, resulting in better stability at such high voltage. The invention discloses that dopants can be co-precipitated during the Na₂CO₃based process by using sulfate solutions such as aluminum sulfate and magnesium sulfate, or suspensions of nano-sized powder. Doping is preferably applied during the precipitation reaction. One embodiment applies nano particle doping. Nano particles can be added as a powder or dispersed into the reactor in a separate feed flow. Alternatively nano particles can be dispersed within the acid or base feed flows. Suitable nano particles are embedded within the growing precipitate particles. Typical examples of nano particles doping are TiO₂, Al₂O₃, MgO, etc. A typically doping by nano particles is at least 500 mol ppm (amount of metal dopant/transition metal) and not more than 2 mol %. In another embodiment doping is performed by adding a dopant solution to the reactor. Salts of Ni, Mn, Mg or Al can be added as separate feed flows, or they can be part of the acid feed. Typical dopant salts are sulfates, nitrates, etc. Typical doping amounts are at least 0.2 mol % (amount of metal dopant/transition metal) and not more than 5 mol %.
Generally speaking, the possibility of doping an aluminum solution into a cobalt carbonate or a cobalt hydroxide carbonate compound is surprising, as not only 3-valent aluminum is not well-matched on a 2-valent cobalt site, but also aluminum dissolves at high pH, and in general the precipitation reaction requires a high pH. Surprisingly aluminum could be doped, i.e. homogeneously distributed at atomic scale, in a cobalt hydroxide carbonate based cobalt compound by a Na₂CO₃based process with almost no loss of aluminum. Additionally, whereas Mg solution doping is difficult or impossible using a bicarbonate process because of the high solubility of Mg²⁺ at low pH, we observe an easy Mg doping using either the Na₂CO₃based precipitation or the Na₂CO₃+NaOH precipitation where the pH is higher.
The cobalt precursor compound obtained by the Na₂CO₃based process under industrial precipitation process conditions contains a high sodium impurity level of 1000 ppm to 3000 ppm. This sodium impurity cannot be removed from the precursor, even not by excessive washing with water. As a high sodium impurity in a cobalt precursor may create undesired phases which are not electrochemically active, this may be a cause of bad electrochemical properties of the cathode material in the final lithium ion battery. LCO—doped or un-doped —which is the cathode material in the lithium ion battery, can be synthesized by a lithiation process of the cobalt hydroxide carbonate based precursor. First, the precursor is mixed with a lithium source—such as lithium carbonate or lithium hydroxide—and certain additives, followed by heating at elevated temperature in an oxygen containing atmosphere, with a suitable heating profile. Finally the sintered material is crushed and sieved. It is expected that the charge and discharge capacities—which are amongst the most important electrochemical properties in a lithium ion battery—decrease as the level of sodium impurity increases. The invention discloses that a sodium impurity can be effectively removed by adding a specific additive before or during lithiation, followed by a heating and washing step. Such additives may be sulfates, such as sodium bisulfate, lithium sulfate, cobalt sulfate, ammonium sulfate, etc. It is important that sufficient sulfate is added so that virtually all sodium is removed in the form of alkali sulfate. As an example −1 mol NaHSO₄can remove 1 mol of Na by washing away Na₂SO₄. Similarly 1 mol of Na can be removed as LiNaSO₄by adding 1 mol of Li₂SO₄. 2 mols of Na can be removed as Na₂SO₄when adding CoSO₄, etc.
Since lithium sodium sulfate is thermodynamically stable, it is formed during lithiation at elevated temperature if a sulfate is added to the cobalt compound, followed by a heat treatment. Therefore, the sulfate can be added during the blending step of the cobalt precursor and the lithium source, and the lithium sodium sulfate is removed by a washing step after firing. Although lithium sulfate and cobalt sulfate are preferred because lithium and cobalt are the main elements in the cathode material, other sulfates such as aluminum sulfate and magnesium sulfate or bisulfates, peroxisulfates etc. can also be a good choice, since some additives deliver positive effects in a cathode material. Alternatively, if a sodium sulfate compound is formed it is water-soluble and can be easily removed by a simple washing step with water.
By applying the technology in this invention: precipitating a cobalt hydroxide carbonate based precursor by a Na₂CO₃based process, and removing the sodium impurity before or during lithiation step, a high quality cathode material which has an improved electrochemical stability and higher energy density can be obtained.
The invention is further illustrated in the following examples:
Description of Analysis Methods
Data about the particle size distribution (PSD) such as D50, D99, and span are preferably obtained by a laser PSD measurement method. In this invention, the laser PSD is measured using a Malvern Mastersizer 2000 with Hydro 2000MU wet dispersion accessory, after dispersing the powder in an aqueous medium. In order to improve the dispersion of the powder in the aqueous medium, sufficient ultrasonic irradiation and stirring are applied and an appropriate surfactant is introduced. Note that as a narrow span is an indicator of a pronounced sphericity of a particle, the value of the span is used in the Examples to measure sphericity.
The specific surface area is measured with the Brunauer-Emmett-Teller (BET) method using a Micromeritics Tristar 3000. 3 g of powder sample is vacuum dried at 300° C. for 1 h prior to the measurement in order to remove adsorbed species before measurement.
The inductively coupled plasma (ICP) method is used to measure the content of elements such as lithium, cobalt, sodium, aluminum and magnesium by using an Agillent ICP 720-ES. 2 g of powder sample is dissolved in 10 mL high purity hydrochloric acid in an Erlenmeyer flask. The flask is covered by glass and heated on a hot plate for complete dissolution of the precursor. After being cooled to room temperature, the solution is moved to a 100 mL volumetric flask that was 3˜4 times rinsed with distilled (DI) water. After filling the flask with the solution, the volumetric flask is filled with DI water up to the 100 mL mark, followed by complete homogenization. 5 mL solution is taken out with a 5 mL pipette and transferred into a 50 mL volumetric flask for a 2^nddilution, where the volumetric flask is filled with 10% hydrochloric acid up to the 50 mL mark and then homogenized. Finally, this 50 mL solution is used in the ICP measurement.
The tap density (TD) measurement is carried out by mechanically tapping a graduated measuring cylinder (100 ml) containing sample (having a mass W of around 60-120 g). After observing the initial powder volume, the measuring cylinder is mechanically tapped for 400 times, so that no further volume (V in cm³) or mass (W) change is observed. The TD is calculated as TD=W/V. The TD measurement is carried out on an ERWEKA® instrument.
The XRD measurement is performed with a Rigaku X-Ray Diffractometer (D/MAX-2200/PC) using Cu Kα. The scan speed is set at continuous scanning at 1 degree per minute. The step-size is 0.02 degree. Scans are performed between 15 and 85 degree. Quantitative phase analysis is carried out using a TOPAS software. For the aim of this invention, the peak intensity P1 is defined as the maximum intensity at 34˜35 degree (corresponding to the (021) peak of the Co₂(OH)₂CO₃structure) without background subtraction and Peak intensity P2 is defined as the maximum intensity at 32×33 degree (corresponding to the (104) peak of the CoCO₃structure) without background subtraction. The peak ratio P is the ratio of P1 to P2.
Cross section analysis is done by a focus ion beam instrument, which is a JEOL (IB-0920 CP). The instrument uses an argon gas as a beam source. A small amount of powder is mixed with a resin and hardener, then the mixture is heated for 10 minutes on a hot plate. After heating, it is placed into the ion beam instrument and the settings are adjusted in a standard procedure, which a voltage is set as 6 kV for 3 hours duration. Scanning Electron Microscopy (SEM) is carried out using a JEOL JSM 7100 F scanning electron microscope. The electron microscope is fitted with a 50 mm²X-MaxN EDS (Energy-dispersive X-ray spectroscopy) sensor from Oxford instruments.
Coin cells that are used in a floating test and for performing a general electrochemical test are assembled by the following steps:
Step 1): preparation of a positive electrode: a slurry that contains the solids: electrochemical active material, conductor (Super P, Timcal) and binder (KF#9305, Kureha) in a weight ratio 90:5:5; and a solvent (NMP, Sigma-Aldrich) is prepared in a high speed homogenizer. The homogenized slurry is spread on one side of an aluminum foil using a doctor blade coater with a 230 μm gap. It is dried in an oven at 120° C., pressed using a calendaring tool, and dried again in a vacuum oven to remove the solvent completely.
Step 2): coin cell assembly: a coin cell is assembled in a glovebox which is filled with an inert gas (argon). For the general electrochemical test, a separator (Celgard) is located between the positive electrode and a piece of lithium foil used as negative electrode. For the floating test, two pieces of separator are located between the positive electrode and the negative material, which consists of graphite. 1M LiPF6 in EC/DMC (ratio 1:2) is used as electrolyte and dropped between separator and electrodes. Then, the coin cell is completely sealed to prevent leakage of electrolyte.
The floating test analyses the stability of cathode materials at high voltage charging at elevated temperature. The prepared coin cell is tested according to the following charge protocol: the coin cell is first charged to 4.5V at constant current mode and C/20 rate (with 1C=160 mAh/g) in a 60° C. chamber, is then kept at constant voltage (4.5V) for 5 days (120 hours), which is a very severe condition. The maximum current is 1 mA. FIG. 1 displays the results of a typical floating test. First the cathode is charged (data not shown) under CC (constant current) mode. As the final voltage is reached the cell is continuously charged under a constant voltage (CV) mode. The graph shows the recorded current where t=0 is the time were the CV mode charging starts. Once side reactions or metal dissolution happen, there will be a voltage drop. The electrochemical instrument will automatically compensate the (lost) current to keep the voltage constant. Therefore the recorded current is a measure of the ongoing side reactions. As shown in FIG. 1, time (in hours) starts from the beginning of the constant voltage charge, the recorded voltage (V—right axis) and current (mA/g—left axis) are respectively represented by the dashed and solid lines. From the change of current, one can observe the degradation of the tested coin cell at high voltage and temperature. At the end, the current of the coin cell reaches the maximum current (1 mA) and the voltage drops due to short circuiting, where this time is recorded as “failure time” (indicated by FT on the Figure) which is a measure of the high voltage stability and the degree of cobalt dissolution of cathode material. After the floating test, the coin cell is disassembled. The anode and separator close to the anode are analyzed by ICP (inductively coupled plasma) for a metal dissolution analysis, since the prior art described that if metal dissolution happens, the dissolved metal will be deposited on the surface of the anode in metal or metal alloy form. The measured cobalt content is normalized by failure time and total amount of active material in the electrode so that the specific cobalt dissolution value can be obtained.
The general electrochemical test of coin cells comprises two parts as follows: (see also Table 1). Part I is the evaluation of rate performance at 0.1C, 0.2C, 0.5C, 1C, 2C and 3C in the 4.3˜3.0V/Li metal window range. The first charge and discharge capacity (CQ1 and DQ1) are measured by constant current mode with 0.1C rate, where 1C is defined as 160 mAh/g. A relaxation time of 30 minutes for the first cycle and 10 minutes for all subsequent cycles is allowed between each charge and discharge. The irreversible capacity Q_irr.is expressed in % as:
$Q_{Irr .} = \frac{(CQ 1 - DQ 1)}{CQ 1} \times 100 (%)$
The rate performance at 0.2C, 0.5C, 1C, 2C and 3C is expressed as the ratio between the retained discharge capacity DQn, with n=2, 3, 4, 5 and 6 for respectively nC=0.2C, 0.5C, 1C, 2C and 3C as follows:
$nC rate = \frac{DQn}{DQ 1} \times 100 (%)$
For example
$3 C rate (in %) = \frac{DQ 6}{DQ 1} \times 100$
Part II is the evaluation of cycle life. The charge cutoff voltage is set as 4.6V/Li metal. The discharge capacity at 4.6V/Li metal is measured at 0.1C at cycles 7 and 31 and 1C at cycles 8 and 32. Capacity fadings at 0.1C and 1C are calculated as follows and are expressed in % per 100 cycles:
$0.1 C QFad . = (1 - \frac{DQ 31}{DQ 7}) \times \frac{10000}{23} in \frac{%}{100} cycles$ $1 C QFad . = (1 - \frac{DQ 32}{DQ 8}) \times \frac{10000}{23} in \frac{%}{100} cycles$

TABLE 1

Testing protocol of coin cell analysis

Charge

Discharge

					V/Li				V/Li
		C	End	Rest	metal	C	End	Rest	metal
Type	Cycle No	Rate	current	(min)	(V)	Rate	current	(min)	(V)

Part I:	1	0.10	—	30	4.3	0.10	—	30	3.0
Rate	2	0.25	0.05 C	10	4.3	0.20	—	10	3.0
performance	3	0.25	0.05 C	10	4.3	0.50	—	10	3.0
	4	0.25	0.05 C	10	4.3	1.00	—	10	3.0
	5	0.25	0.05 C	10	4.3	2.00	—	10	3.0
	6	0.25	0.05 C	10	4.3	3.00	—	10	3.0
Part II:	7	0.25	0.10 C	10	4.6	0.10	—	10	3.0
cycle life	8	0.25	0.10 C	10	4.6	1.00	—	10	3.0
	9-30	0.25		10	4.6	0.50	—	10	3.0
	31	0.25	0.10 C	10	4.6	0.10	—	10	3.0
	32	0.25	0.10 C	10	4.6	1.00	—	10	3.0

The invention is further illustrated in the following examples:

Example 1

Example 1 is explanatory and discusses the benefits of a well-shaped precursor. The advantages of using large cobalt precursors that have a narrow span are that: 1) a simplified lithiation process is possible, 2) the final cathode material can have a high packing density, and 3) there will be less problems when making a positive electrode using the final cathode material such as less electrode crushing and scratching.
Conventional LCO is generally made from a cobalt precursor that has a small particle size—the median particle size being around 5 μm—and wide span. The particle size of LCO is directly linked to the electrode density, and a median particle size of 15 to 20 μm is a most popular range in conventional LCO. To grow the particle size from 5 μm for the cobalt precursor to 20 μm for the final LCO, either 1) an extremely high energy input is required—by applying a very high heating temperature and/or a very long heating time—or 2) a high lithium to cobalt ratio (Li/Co) is needed. For the second option, since LCO has the best electrochemical properties near its stoichiometric composition, an additional high temperature heating process is required using extra cobalt precursor to adjust the Li/Co ratio to 1. The conclusion is that when a cobalt precursor having a small particle size is used, neither of these two options is efficient at industrial scale in respect of production cost.
Table 2 shows the physical property of LCO as a function of the choice of cobalt precursors having different PSD. CEX1-P is a conventional cobalt precursor (battery grade Co₃O₄from Umicore) which has a small particle size and wide span, while EX1-P is a cobalt precursor (Co₃O₄from Yacheng New Materials) which has a large particle size with narrow span. EX1-C-1, EX1-C-2, CEX1-C-1, and CEX1-C-2 are synthesized in a lithiation process by blending the different cobalt precursors with lithium carbonate for different Li/Co ratios, heating at 980° C. for 10 hours in air atmosphere, crushing by a milling tool, and sieving by an ASTM standard 270 mesh sieve.

TABLE 2

Property of LCO as a function of property of cobalt precursor

	Lithiation
	condition	PSD	Surface

Product	Product	Cobalt		D50	D99		area
ID	type	precursor	Li/Co	μm	μm	Span	m²/g

EX1-P	Cobalt			18.11	31.09	0.66	4.34
CEX1-P	precursor			3.78	10.34	1.74	1.20
EX1-C-1	LCO	EX1-P	1.015	18.06	38.60	0.65	0.16
EX1-C-2			1.030	18.59	39.35	0.66
CEX1-C-1		CEX1-P	1.035	7.06	15.96	1.04	0.30
CEX1-C-2			1.055	17.32	51.08	1.52	0.17

A low surface area of LCO can indicate that the internal porosity of LCO is smaller for a comparable PSD. The internal porosity of LCO should be as small as possible to get the highest density of LCO. This is achieved by the long sintering time and high sintering temperature of the lithiation process. It is observed that a higher Li/Co (1.055 for CEX1-C-2) is required to get a similar D50 and surface area when CEX1-P is used, compared to 1.015 for EX1-C-1 using precursor EX1-P. Since it is expected that the electrochemical property of CEX1-C-2—more particularly cycle life—is much worse than that of EX1-C-1, CEX1-C-2 requires the additional high temperature heating step with extra cobalt precursor to decrease Li/Co.
A smaller D99 of the final product, as well as a simplified lithiation process are some of the big advantages when using large spherical cobalt precursors having a narrow span. D99 is a good parameter to estimate the maximum particle size. When D99 is very big, it is expected that there is a problem for the surface quality of the positive electrode since big particle can scratch the electrode surface during the electrode coating process. From this perspective, the ratio D99/D50 of LCO is very important since a lower D99 can limit the need to increase D50, even though a higher D50 is preferable to increase the electrode density. For example, CEX1-C-2 has a much higher D99 than EX1-C-1 in spite of having a similar D50. Therefore, shaped narrow span cobalt precursors—thus having a low D99/D50 —can have a high D50 without concerns about the absolute value of D99, resulting in having the possibility to increase the electrode density further by increasing the particle size.

Example 2

Example 2 illustrates the Na₂CO₃based co-precipitation process. A schematic illustration of the process is shown in FIG. 2. In FIG. 2, the following is shown:
Flows: F1: dopant; F2: CoSO₄; F3: Na₂CO₃; F4: Slurry; F5: Clear filtrate out; F6: thickening slurry
Apparatus: R1: precipitation reactor; R2: settlement reactor; R3: peristaltic pump
Na₂CO₃and CoSO₄solutions with a concentration of 2 mol/L are separately prepared. The precipitation is carried out in a 4L reactor at elevated temperature (referred to as T1 hereafter) with an impeller stirring speed of 1000 RPM. The CoSO₄solution is pumped first in the reactor for 20 minutes without adding Na₂CO₃solution. Then, more CoSO₄solution is continuously pumped in the precipitation reactor together with the Na₂CO₃solution at double flow rate for 20 minutes. After that (40 minutes in total), the flow rate of CoSO₄and Na₂CO₃solution is kept constant with a CO₃/Co molar ratio of 1.08. Two different methods to introduce dopants are used in the invention. One way (referred to as DM1 hereafter) is to dissolve a sulfate—such as aluminum sulfate and magnesium sulfate—in a CoSO₄solution with a certain molar ratio so that the dopant can be injected together with CoSO₄. The other way (referred to as DM2 hereafter) is to manually inject a suspension of the dopant directly in the reactor during the precipitation, and a certain amount of the suspension is injected once an hour to get a certain molar ratio of dopant to cobalt. Different from a conventional continuous precipitation process, a first slurry containing precipitated cobalt hydroxide carbonate precursor is discharged from the precipitation reactor through overflow and goes to a second 3L settlement reactor. In the settlement reactor, the solid precipitate settles down to the bottom since the stirring speed is mild (less than 200 RPM), resulting in a solid-liquid separation. The settled thick slurry at the bottom of the settlement reactor is pumped back into the precipitation reactor. The precipitation is stopped once the particle size of the precipitates in the reactor reaches the target particle size or once the span of the precipitate starts increasing (whichever is first), where the “precipitation time” is defined as the time between starting to inject any solution into the reactor and stopping the precipitation. The precursor is collected by emptying both the precipitation and settlement reactors. Then, a solid-liquid separation of the obtained precursor slurry takes place in a press filter, where the obtained solid is washed with deionized water several times. Finally, the precursor is dried at an elevated temperature to remove any remaining deionized water.

Example 3

Example 3 describes the doped cobalt hydroxide carbonate precursor compound. Table 3 and FIGS. 3 and 4 show the physical and chemical properties of the precursors, precipitated as described in Example 2, except for EX3-P-6 to 8, CEX3-P-2 and CEX3-P-3. Each precursor is precipitated with different resident and/or total precipitation times to show the influence on the particle size. CEX3-P-3 is a pure cobalt carbonate precipitated by a NH₄HCO₃process without dopant as a control product, where 1.2 mol/L CoCl₂and 2.5 mol/L NH₄HCO₃are used in a 10 L reactor and filtered precipitates are dried at 75° C. The precipitation temperature T1 for CEX3-P-2 and CEX3-P-3 is 60° C. while for the other products it is 90° C.

TABLE 3

Physical and chemical property of cobalt hydroxide carbonate based cobalt precursors

ICP

EDS

XRD

PSD

Al/

Mg/

Ti/

Peak

Tap

T1

Doping

D50

Co

Na

Co

ratio

density

Product ID	Base	(° C.)	method	(μm)	SPAN	(wt. %)	(wt. %)	(% in mol/mol)	P1/P2	(g/cm³)

EX3-P-1	Na₂CO₃	90	—	17.3	0.64	55.99	0.12	—	—	—	0.17	1.46
EX3-P-2	Na₂CO₃	90	DM1	20.7	0.64	54.06	0.10	0.92	—	—	0.10	1.94
EX3-P-3	Na₂CO₃	90	DM2	22.9	0.67	52.33	0.23	1.21	—	—	0.73	2.35
EX3-P-4	Na₂CO₃	90	DM1	18.5	0.76	53.64	0.10	0.98	0.95	—	0.13	1.25
EX3-P-5	Na₂CO₃	90	DM2	12.1	0.68	53.94	0.12	0.81	—	0.49	—	1.82
EX3-P-6	Na₂CO₃+	90	—	21.3	0.62	53.00	0.09	—	—	—	0.09	2.17
	NaOH
EX3-P-7	Na₂CO₃+	90	DM1	29.5	0.61	53.37	0.12	—	1.00	—	0.07	2.35
	NaOH
EX3-P-8	Na₂CO₃+	90	DM1	27.9	0.68	53.95	0.13	—	1.02	—	0.08	2.15
	NaOH
CEX3-P-1	Na₂CO₃	90	DM1	14.6	0.68	50.79	0.33	0.96	—	—	3.77	2.22
CEX3-P-2	Na₂CO₃	60	—	14.0	1.45	59.74	1.90	—	—	—	—	0.43
CEX3-P-3	NH₄HCO₃	60	—	20.9	0.65	46.54	0.02	—	—	—	33.1	2.13

XRD

Precipitation condition

	Quantitative phase analysis		Peak			Precipitation
	(%)		ratio	Base/	RT	time

Product ID	CoCO₃	Co₂(CO₃)(OH)₂	P1/P2	acid	(hour)	(hour)

EX3-P-1	0	100	0.17	1.08	2.74	6.0
EX3-P-2	0	100	0.10	1.08	2.74	19.0
EX3-P-3	25	75	0.73	1.08	2.74	58.0
EX3-P-4	0	100	0.13	1.10	2.74	6.0
EX3-P-5	—	—	—	1.08	2.74	13.0
EX3-P-6	0	100	0.09	1.08	2.74	19.0
EX3-P-7	0	100	0.07	1.08	2.74	25.5
EX3-P-8	0	100	0.08	1.08	2.74	30.0
CEX3-P-1	57	43	3.77	1.08	4.11	40.0
CEX3-P-2	—	—	—	1.08	2.74	6.0
CEX3-P-3	100	0	33.10		3.00

The target dopant content for EX3-P-2 to 5, EX3-P-7 to 8, and CEX3-P-1 is 1.0 mol % for Al and Mg, and 0.5 mol % for Ti. The obtained contents (from ICP or EDS analysis) are close to the target, with marginal deviations that can easily be adjusted. It is confirmed that both methods for introducing dopants—dissolving aluminum or magnesium sulfate in the cobalt sulfate solution (DM1) and injecting a suspension of nano-sized dopant into the precipitation reactor periodically (DM2)—work well. All products have a narrow span except CEX3-P-2. EX3-P-6 and EX3-P-7 are precipitated using 90 vol % of 2 mol/L Na₂CO₃solution and 10 vol % of 4 mol/L NaOH solution as a base, and the other process parameters according to Example 2. EX3-P-8 is precipitated using 60 vol % of 2 mol/L Na₂CO₃solution and 40 vol % of 4 mol/L NaOH solution as a base, and the other process parameters according to Example 2. It is observed that EX3-P-6 to 8 which are precipitated by mixtures of Na₂CO₃and NaOH as a base solution have relatively low Na contents compared to other products.
Each product EX3-P-1 to 8 can be used as a cobalt precursor of LCO depending on the characteristic of these products such as PSD, dopants concentration, and tap density. For example, a small fraction of EX3-P-5 which has smaller particle size can be blended as a “filler precursor” with a large fraction of EX3-P-3 as a “coarse precursor” to increase the volumetric powder density of LCO. CEX3-P-2, precipitated at a too low temperature, results in a span and Na content that is too high, and a tap density that is too low. CEX3-P-3 made by the traditional ammonium bicarbonate process results in a very low Na content, low span and high D50, but the morphology of the obtained pure CoCo₃is not good, and this has a negative impact on the final LCO.
The cobalt content and quantitative phase analysis by XRD indicate that all products obtained by the Na₂CO₃based process are composed of cobalt hydroxide carbonate (Co₂(OH)₂CO₃), which belongs to the malachite-rosasite mineral group, and some additionally contain cobalt carbonate. The XRD peak ratio (021) over (104) can be used as a criteria to quantify the relative amount the different crystal structures. The malachite-rosasite mineral group is a monoclinic or triclinic metal hydroxide carbonates with the general formula A₂(OH)₂CO₃or AB(OH)₂CO₃, where A and B is either cobalt, magnesium, copper, nickel or zinc, as described in “Fleischer's Glossary of Mineral Species” (J. A. Mandarino, The Mineralogical Record Inc., Tucson, 1999). The crystallography of the cobalt hydroxide carbonate in this invention shows good agreement with that of Pokrovskite as described in “The malachite-rosasite group: crystal structures of Glaukosphaerite and Pokrovskite” (Perichiazzi. N et al., European Journal of Mineralogy, 2006).
FIG. 4 shows the relation between the proportion of the cobalt hydroxide carbonate phase in the precipitate, and the amount of sodium impurity (Na content in wt % obtained by ICP versus Co₂(OH)₂CO₃content in wt % obtained by Rietveld XRD analysis). It is observed that the sodium impurity decreases as the proportion of cobalt hydroxide carbonate phase increases. Both EX3-P-2 and CEX-P-1 are prepared with the same general process parameters (the base/acid molar ratio is the same as the CO₃/Co ratio), except for the residence (RT) and precipitation time, where it can be observed that when increasing these times the hydroxy-carbonate phase is converted to the carbonate phase, and the obtained precursor does not permit to achieve the objectives of the invention. In Example 6 the treatment of a high sodium content precursor is described.
To verify how well Al is distributed in a particle, an EDS (Energy dispersive X-ray spectroscopy) analysis is performed after cutting particles by using the cross section method as described in “Description of analysis methods”. The upper left figure in FIG. 5a is a SEM image of a cross section of EX3-P-3 and the upper right figure shows the EDS mapping result of EX3-P-3, where white points indicate a homogeneous presence of Al. An enlarged view of this EDS map is repeated in FIG. 5b . Since there is a clear Al peak in the spectrum, the white points in upper right figure and FIG. 5b are not caused by noise. Three different zones (Z1, Z2, and Z3), as shown in the upper left figure in FIG. 5a , are separately measured by EDS measurements and Table 4 shows the analysis result. Based on the Al contents of these zones and the result of the EDS mapping, it is clear that Al is homogeneously distributed in a particle of EX3-P-3.

TABLE 4

Al contents at different positions, measured by EDS

		Al/Co
	Position	(% in mol/mol)

	Z1	1.42
	Z2	1.50
	Z3	1.43

Example 4

Example 4 describes the synthesis of LCO with the precursors of Example 3: EX3-P-3 and CEX3-P-3 are lithiated to form lithium cobalt oxides. These cobalt compounds are blended with lithium carbonate with different lithium to metal (Li/M) ratios, where M is the sum of cobalt and aluminum. Each blend is heated at 1000° C. for 12 hours. Then, the sintered materials are crushed. For improving the electrochemical properties, titanium oxide is blended with the obtained materials and the resulting “second” blends are heated at 750° C. for 6 hours. Table 5 shows the failure time and specific cobalt dissolution from floating test as a function of the type of cobalt precursor and the Li/M molar ratio. For the LCO products made from EX3-P-3, the failure time increases as the Li/M ratio increases. This is because the cobalt dissolution is less due to the presence of more lithium, resulting in a better high voltage stability. The example shows that LCO products made from an aluminum doped cobalt hydroxide carbonate precursor (EX3-P-3) have a much longer failure time and less cobalt dissolution than those from non-doped pure cobalt carbonate produced by the NH₄HCO₃process. Working with a cobalt hydroxide carbonate precursor is thus not only interesting from a cost perspective, but also this Example indicates that the presence of aluminum in LCO is beneficial to have a better high voltage stability.

TABLE 5

Floating test result of aluminum doped LCO and non-doped LCO

Floating test

			Failure	Specific
			time	Co
Product ID	Precursor	Li/(Co + Al)	(hour)	(mg/g/h)

EX4-C-1	EX3-P-3	1.000	42.0	0.64
EX4-C-2		1.015	88.0	0.65
EX4-C-3		1.030	120.0	0.49
CEX4-C-1	CEX3-P-3	0.990	30.2	1.57
CEX4-C-2		1.010	25.2	1.06
CEX4-C-3		1.030	22.5	0.86

Specific Co: the measured cobalt content is normalized by failure time and total amount of active material in the electrode so that the specific cobalt dissolution value can be obtained.

Example 5

To identify the need of homogeneous aluminum doping compared to aluminum surface coating on a cobalt precursor, two LCO products are synthesized by using 1) an aluminum doped cobalt hydroxide carbonate based precursor (being EX3-P-3) mixed with 15 wt % of EX3-P-5 as a filler material before lithiation and 2) 1 mol % aluminum oxide coated Co₃O₄precursor (from Yacheng New Materials) mixed with 15 wt % of EX3-P-5 as a filler material before lithiation. This also illustrates that one of the practical uses of large spherical cobalt precursors with narrow span is to increase the packing density by blending with smaller particles so that smaller particles can occupy the voids—as a “filler” material—created by the close packing of the large spherical particles. Then, lithium carbonate is blended with the pre-blended cobalt precursors, where Li/M ratio is 1.005, and the blends are heated at 1000° C. for 12 hours. The obtained materials are crushed and sieved on a 270 mesh sieve. Table 6 shows the floating test results of the LCO products, where EX5-C is produced from an aluminum doped hydroxide carbonate based cobalt precursor and CEX5-C is produced by an alumina coated Co₃O₄precursor. It is observed that EX5-C has a much higher failure time and lower specific cobalt dissolution compared to CEX5-C, indicating that when Al is added, it should be homogeneously distributed in LCO by means of doping, instead of surface coating, to be able to benefit from the positive influence of the dopant on the structural stability of LCO. The difference in Co dissolution is not caused by the difference in nature of the precursor itself (hydroxy-carbonate versus cobalt oxide) since without doping or coating both of these have a similar Co dissolution problem.

TABLE 6

Floating test result of aluminum coated LCO and
aluminum doped LCO

Floating test

		Failure	Specific
		time	Co
Product ID	Large precursor	(hour)	(mg/g/h)

EX5-C	Al doped	76.7	0.80
CEX5-C	Al₂O₃coated	28.5	1.06

Example 60

In Example 6 the removal of the sodium impurity is illustrated. In Example 3 it was shown that the sodium content of the precursor can be from 0.10% to 0.33%, which may be detrimental for the LCO application. EX4-C-1 and EX4-C-3 are produced from EX3-P-3 which contains 0.23% of sodium. Table 7 shows the sodium content and electrochemical property of EX4-C-1 and 3, measured by the general electrochemical test of coin cells described before. It is observed that the sodium content of LCO products is the same as that of cobalt compounds, indicating that sodium remains after lithiation. Due to the high sodium content, the charge and discharge capacities (CQ1 and DQ1) are lower than expected.
Sodium can be effectively removed by the following procedure during lithiation, and an additional washing process. EX3-P-3 is blended with lithium carbonate and lithium sulfate, where the amount of added lithium sulfate is the same as the amount of sodium: molar ratio Na:Li₂SO₄=1:1, and lithium carbonate is added to match the target Li/M ratio (1.00 or 1.03 in this example). Heating and post treatment conditions are same as the conditions of EX4-C-1 and 3, described in Example 4. After the post treatment, the obtained LCO products are washed with water, followed by drying in an oven at elevated temperature after filtering. Finally, two LCO products —EX6-CW-1 and EX6-CW-2—are obtained. As can be seen in Table 7, EX6-CW-1 and 2 have a significantly reduced sodium content, resulting in improved electrochemical property such as CQ1, Q_irr, DQ1, and 3C rate, and keeping the same cycle stability.

TABLE 7

Sodium content and electrochemical property of LCO before and after removing
sodium impurity

Coin cell test

		ICP					0.1C	1C
	Li/	Na	CQ1	DQ1	Q_irr.	3C rate	Q fad.	Q fad.
Product ID	(Co + Al)	%	mAh/g	mAh/g	%	%	%/100	%/100

EX4-C-1	1.00	0.24	162.6	156.0	4.0	88.6	57.0	82.9
EX4-C-3	1.03	0.23	160.9	148.4	7.8	81.7	64.7	89.8
EX6-CW-1	1.00	0.01	163.7	158.9	2.9	92.4	62.4	86.5
EX6-CW-2	1.03	0.01	162.7	157.5	3.2	88.6	53.3	84.9

Claims

1-16 (canceled)

17. Use of a cobalt based hydroxide carbonate compound, having a malachite-rosasite mineral structure as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries.

18. Use of the cobalt based hydroxide carbonate compound of claim 17, wherein the compound has the general formula [Co_1-aA_a]₂(OH)₂CO₃, A being one or more of Ni, Mn, Al, Ti, Zr and Mg, with a≤0.05.

19. Use of the cobalt based hydroxide carbonate compound of claim 17 in a mixture with cobalt carbonate, wherein in the XRD pattern of the mixture the peak ratio P has a value <1, with P=P1/P2, P1 being the maximum peak intensity at 32˜33 degree, and P2 being the maximum peak intensity at 34˜35 degree.

20. Use of the cobalt based hydroxide carbonate compound of claim 17, wherein the compound further comprises Na as an impurity of up to 0.3 wt %.

21. Use of the cobalt based hydroxide carbonate compound of claim 17, wherein the compound has a particle size distribution with D50 between 15 and 25 μm and a span <0.80.

22. Use of the cobalt based hydroxide carbonate compound of claim 17, wherein the compound has a spherical morphology and a tap density >1.8 g/cm³.

23. Use of the cobalt based hydroxide carbonate compound of claim 18, wherein A is one or both of Al and Mg, with 0.002≤a≤0.020, and wherein one or both of Al and Mg is homogeneously doped in the compound.

24. A precursor of a lithium cobalt based oxide comprising a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure.

25. The precursor of claim 24, wherein the compound has the general formula [Co_1-aA_a]₂(OH)₂CO₃, A being one or more of Ni, Mn, Al, Ti, Zr and Mg, with a≤0.05.

26. The precursor of claim 24, further comprising cobalt carbonate, wherein the cobalt carbonate is mixed with the cobalt based hydroxide carbonate compound to form a mixture, and in the XRD pattern of the mixture the peak ratio P has a value <1, with P=P1/P2, P1 being the maximum peak intensity at 32˜33 degree, and P2 being the maximum peak intensity at 34˜35 degree.

27. The precursor of claim 24, wherein the compound further comprises Na as an impurity of up to 0.3 wt %.

28. The precursor of claim 24, wherein the compound has a particle size distribution with D50 between 15 and 25 μm and a span <0.80.

29. The precursor of claim 24, wherein the compound has a spherical morphology and a tap density >1.8 g/cm³.

30. The precursor of claim 25, wherein A is one or both of Al and Mg, with 0.002≤a≤0.020, and wherein one or both of Al and Mg is homogeneously doped in the compound.