CN109696520B - Co in lithium ion battery positive active material 3 O 4 Content determination method - Google Patents
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Abstract
Co in lithium ion battery anode active material 3 O 4 The content determination method comprises the following steps: (1) Adding an impregnating agent into a sample to be measured, adding a metal ion salt solution, and fully stirring and dissolving to obtain a solution a; (2) Filtering the solution a obtained in the step (1), and cleaning residues on a filter membrane after the filtration is finished; (3) Adding the residue obtained in the step (2) and the filter membrane into the strong acid solution, and completely stripping the residue on the filter membrane into the strong acid solution to obtain a mixed solution b of the residue and the strong acid solution; (4) Adding a strong acid solution into the mixed solution b in the step (3), heating, evaporating and drying; (5) cooling and then fixing the volume to obtain a solution c; (6) The content of Co in the solution c was measured and converted into Co 3 O 4 Value, namely obtaining Co in the sample to be measured 3 O 4 The content of (a). The method can accurately measure the content of the residual cobaltosic oxide in the lithium ion battery anode active material.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to Co in a positive electrode material 3 O 4 And (4) a content detection method.
Background
The lithium ion battery has the advantages of light weight, high specific energy, no memory effect, no pollution, small self-discharge, long service life and the like, is widely applied to civil and military fields such as mobile phones, notebook computers, video cameras, digital cameras and the like, and also shows good development prospect in the aspects of electric automobiles, spaceflight and energy storage.
Co is usually added into the lithium ion battery anode material as a modified substance, and Co may remain in the anode material 3 O 4 . However, as is well known, co 3 O 4 High concentration Co remained on the surface of the positive electrode material without activity in the charge and discharge process 3 O 4 The method has the advantages that the charge and discharge capacity is influenced, and the charge and discharge capacity is reduced, so that the control of the residual Co amount on the surface of the anode material is very important for improving the performance of lithium cobaltate, and in the prior art, no good detection means is provided for the residual Co in the anode material.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art and provide a method for accurately measuring Co in the lithium ion battery anode active material 3 O 4 And (4) a content detection method. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
co in lithium ion battery anode active material 3 O 4 The content determination method comprises the following steps:
(1) Adding a wetting agent into a sample to be measured, adding a metal ion salt solution, and fully stirring and dissolving to obtain a solution a;
(2) Filtering the solution a obtained in the step (1), and cleaning residues on a filter membrane after the filtration is finished;
(3) Adding the residues in the step (2) and the filter membrane into a strong acid solution, and completely stripping the residues on the filter membrane into the strong acid solution to obtain a mixed solution b of the residues and the strong acid solution;
(4) Adding a strong acid solution into the mixed solution b in the step (3), heating, evaporating and drying;
(5) Cooling and fixing the volume to obtain a solution c;
(6) The content of Co in the solution c was measured and converted to Co 3 O 4 Value to obtainTo Co in the sample to be determined 3 O 4 The content of (a).
In the above measurement method, it is preferable that the step (4) is repeated at least once before the step (5) is performed. The repetition is performed at least once to improve the accuracy of the data.
In the above measurement method, the wetting agents are preferably HCl or H 2 SO 4 And H 3 PO 4 And at least contains H 2 SO 4 Or H 3 PO 4 Or both. The metal ion salt solution is NiSO 4 、NiCl 2 、MnSO 4 、 MnCl 2 、FeSO 4 、FeCl 2 、Cu 2 SO 4 、CuCl 2 、CrSO 4 And CrCl 2 One or more of (a). The impregnating agent and the metal salt solution (mainly having the functions of reduction and replacement) are added into the sample to dissolve and remove LiCoO in the sample 2 Filtering to obtain Co-containing material 3 O 4 The residue of (2).
In the above measurement method, the strong acid is preferably one or more of nitric acid, hydrochloric acid and aqua regia, and the mass concentration of the nitric acid, hydrochloric acid and aqua regia is preferably 30 to 70%.
In the above measurement method, in the step (1), the stirring time is preferably 0.5 to 2 hours. The stirring time has a certain influence on the test results and needs to be reasonably controlled.
In the above measurement method, the stirring time is preferably 0.8 to 1.4 hours.
In the above determination method, preferably, the lithium ion battery positive electrode active material is lithium cobalt metal oxide powder, the lithium cobalt metal oxide powder has a coating structure, and the lithium cobalt metal oxide powder includes a lithium cobalt metal oxide matrix and Co 3 O 4 A coating layer of the general formula Li a Co 1-x-y M x N y O 2 ·rCo 3 O 4 Wherein r is more than 0.002 and less than or equal to 0.05, a is more than or equal to 1 and less than or equal to 1.1, x is more than or equal to 0 and less than or equal to 0.02, y is more than or equal to 0 and less than or equal to 0.005, a is more than 1 and 3r, M is a doping element, N is a coating element. In the above formula, if 1+ < 3r < a, the cycle performance of the lithium cobalt metal oxide powder cannot be guaranteed. The cobalt ion in the lithium cobalt metal oxide powder is excessive, and the excessive cobalt ion is Co 3 O 4 In the form of excess Co 3 O 4 The presence of (A) can prevent LiCoO on the one hand 2 Contact with the electrolyte to prevent LiCoO as the positive electrode material 2 The surface of the anode material slowly reacts with the electrolyte to reduce the performance of the anode material, and can reduce Co under the high-voltage condition 4+ Reducing Co at higher cut-off voltage 4+ And the side reaction with the electrolyte can improve the cycle performance of the material. But Co 3 O 4 High concentration Co remained on the surface of the positive electrode material without activity in the charge and discharge process 3 O 4 The charge and discharge capacity is influenced, and the charge and discharge capacity is reduced, so that the content of the carbon nano-particles is obtained by quantitative detection and analysis.
In the above measuring method, it is preferable that excess Co is present in both the inner and outer surfaces of the lithium cobalt metal oxide matrix 3 O 4 Co inside the lithium cobalt metal oxide matrix 3 O 4 With Co of the outer surface 3 O 4 Is less than 1. The Co 3 O 4 Co in spinel phase 3 O 4 The residual lithium content on the outer surface of the lithium cobalt metal oxide matrix is less than or equal to 0.05 percent.
In the above measurement method, preferably, M is one or more of Mg, ca, cu, al, B, ti, Y and Zr, and N is one or more of Na, K, mg, ca, cu, al, B, ti, Y, zr, ni and Mn. More preferably, M is one or two of Mg and Al, and N is one or two of Mg and Ti.
In the above-mentioned measuring method, in the step (1), the impregnating agent and the metal salt solution (mainly having the reducing and replacing functions) are first added to the sample to dissolve and remove LiCoO in the sample 2 Filtering to obtain Co-containing 3 O 4 The residue of (4) and the addition of an acid solution in the steps (3) and (4) are intended to dissolve Co 3 O 4 Obtaining solution containing Co, evaporating to remove acid solution, fixing volume,measuring the content of Co, and converting into Co 3 O 4 Value, namely obtaining Co in the sample 3 O 4 The content of (a).
With FeSO 4 For example, the reaction occurring in step (1) is as follows:
2LiCoO 2 +4H 2 SO 4 +2FeSO 4 ＝Li 2 SO 4 +2CoSO 4 +Fe 2 (SO 4 ) 3 +4H 2 O。
compared with the prior art, the invention has the advantages that: the determination method is simple, raw materials used in the determination are easy to obtain, the content of residual cobaltosic oxide in the lithium ion battery positive electrode active material can be accurately determined by the determination method, the amount of the residual cobaltosic oxide can be accurately controlled, and theoretical guidance is provided for balance of cycle performance and capacity performance of the lithium ion battery positive electrode active material.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an XRD pattern of the positive active material for a lithium ion battery prepared in example 1.
Fig. 2 is an XRD pattern of the positive active material for a lithium ion battery prepared in example 2.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
co in lithium ion battery anode active material 3 O 4 The content determination method comprises the following steps:
(1) Adding a certain amount of lithium ion battery positive active material (LiCo molecular formula) 0.99 Mg 0.01 O 2 ·rCo 3 O 4 ) Adding NiSO 4 And H 2 SO 4 Magnetically stirring the solution to dissolve for 1.5 hours to obtain a solution a;
(2) Filtering the solution a obtained in the step (1) by suction filtration, keeping the filtration state unchanged after the filtration is finished, and washing the residue on the filter membrane by pure water;
(3) Adding the residues obtained in the step (2) and the filter membrane into a nitric acid (with the mass concentration of 30%) solution, ultrasonically stripping the residues from the filter membrane, taking out the filter membrane by using tweezers, and washing a trace amount of residues adhered to the filter membrane into the nitric acid solution by using deionized water to obtain a mixed solution b of the residues and the nitric acid;
(4) Adding a nitric acid solution into the mixed solution b in the step (3), heating, and evaporating and drying the solution;
(5) Repeating the step (4) once after cooling, and fixing the volume to obtain a solution c after cooling again;
(6) Measuring the Co content in the solution c (the measuring method may be atomic absorption or other common methods), and converting into Co 3 O 4 Value, i.e. LiCo 0.99 Mg 0.01 O 2 ·rCo 3 O 4 Middle Co 3 O 4 The content of (b).
In this example, co 3 O 4 Is tested to be 1088ppm, and r =0.0005 is obtained by calculation, namely the molecular formula is LiCo 0.99 Mg 0.01 O 2 ·0.0005Co 3 O 4 。
In this embodiment, the preparation method of the positive electrode active material for the lithium ion battery includes the following steps:
(1) According to the formula Li 1.06 Co 0.99 Mg 0.01 O 2 Weighing the materials, mixing uniformly, and sintering in a bell jar furnace capable of introducing air. Wherein, the precursor containing lithium is lithium carbonate, and the precursor containing cobalt is Co with D50 of 15 μm 3 O 4 The Mg-containing precursors are respectively corresponding oxides, the sintering temperature is 1030 ℃, the sintering time is 10h, and the whole sintering process is carried out in the air atmosphere. And (3) sieving and crushing the sintered lithium cobaltate to obtain the lithium cobaltate CO-A.
(2) LiCo according to the molecular formula 0.99 Mg 0.01 O 2 ·rCo 3 O 4 Mixing CO-A with different amounts of Co (OH) 2 And after uniform mixing, putting the mixture into a bell jar furnace which can be ventilated with air to carry out sintering treatment to obtain the lithium ion battery anode active material. Wherein the sintering temperature is 900 ℃, the sintering time is 10h, and Co (OH) 2 D50 of (2) is 0.8. Mu.m.
FIG. 1 is an XRD representation of the positive electrode active material of the lithium ion battery obtained in example 1, from which it can be seen that the crystal obtained in example 1 is a pure-phase layered lithium cobalt oxide, illustrating that the addition of excess Co during the second sintering absorbs excess Li in the matrix of the first sintering and produces LiCoO 2 On the one hand on residual Co 3 O 4 Under the condition that the content is not very high, the discharge specific capacity of the material is improved, and on the other hand, excessive Li in the matrix is absorbed by Co, so that the flatulence of the material is reduced under the high-temperature condition, and the safety performance and the high-temperature performance of the material are improved.
Example 2:
co in lithium ion battery positive active material 3 O 4 The content determination method comprises the following steps:
(1) Adding a certain amount of lithium ion battery positive active material (LiCo molecular formula) 0.975 Al 0.02 Mg 0.005 O 2 ·rCo 3 O 4 ) Adding MnSO 4 And H 3 PO 4 Dissolving in HCl solution under magnetic stirring for 1.0h to obtainTo solution a;
(2) Filtering the solution a obtained in the step (1) by suction filtration, keeping the filtration state unchanged after the filtration is finished, and washing the residue on the filter membrane by pure water;
(3) Adding the residues obtained in the step (2) and the filter membrane into a nitric acid (with the mass concentration of 70%) solution, ultrasonically stripping the residues from the filter membrane, taking out the filter membrane by using tweezers, and washing a trace amount of residues adhered to the filter membrane into the nitric acid solution by using deionized water to obtain a mixed solution b of the residues and the nitric acid;
(4) Adding a nitric acid solution into the mixed solution b in the step (3), heating, and evaporating and drying the solution;
(5) Repeating the step (4) once after cooling, and fixing the volume to obtain a solution c after cooling again;
(6) Measuring the Co content in the solution c (the measuring method may be atomic absorption or other common methods), and converting into Co 3 O 4 Value, i.e. LiCo 0.975 Al 0.02 Mg 0.005 O 2 ·rCo 3 O 4 Middle Co 3 O 4 The content of (b).
In this example, co 3 O 4 The content of (b) is 21000ppm, and r =0.0105 is calculated, namely the molecular formula of LiCo 0.975 Al 0.02 Mg 0.005 O 2 ·0.0105Co 3 O 4 。
In this embodiment, the preparation method of the positive electrode active material for the lithium ion battery includes the following steps:
(1) According to the formula Li 1.04 Co 0.98 Al 0.02 O 2 Weighing the materials, mixing uniformly, and sintering in a bell jar furnace with air. Wherein the lithium-containing precursor is lithium carbonate, and the cobalt-containing precursor is Co with D50 of 17 μm 3 O 4 Precursors containing Al are respectively Al 2 O 3 The sintering temperature is 1050 ℃, the sintering time is 10h, and the whole sintering process is carried out in the air atmosphere. And (3) screening and crushing the sintered lithium cobaltate to obtain the lithium cobaltate LCO-B1.
(2) Push buttonLiCo of formula 0.975 Al 0.02 Mg 0.005 O 2 ·rCo 3 O 4 Mixing LCO-B1 with varying amounts of Co 3 O 4 Mixing, adding MgO with the proportion of 0.5 mol percent, uniformly mixing, putting into a bell jar furnace capable of introducing air, and sintering to obtain the lithium ion battery anode active material. Wherein the sintering temperature is 900 ℃, the sintering time is 10h 3 O 4 D50 of (b) is 3 μm of agglomerated particles, and D50 of primary particles is less than 1 μm.
FIG. 2 is an XRD pattern of the lithium ion battery positive electrode active material obtained in example 2, and it can be seen from the XRD pattern that as the residual Co content increases, a spinel phase of Co begins to appear 3 O 4 Diffraction peaks indicating the presence of residual Co in the form of spinel phase Co 3 O 4 。
Example 3:
co in lithium ion battery anode active material 3 O 4 The content determination method comprises the following steps:
(1) Adding a certain amount of lithium ion battery positive active material (LiCo molecular formula) 0.975 Al 0.02 Ti 0.005 O 2 ·rCo 3 O 4 ) Adding FeSO 4 And H 2 SO 4 +H 3 PO 4 Magnetically stirring and dissolving the solution for 0.8h to obtain a solution a;
(2) Filtering the solution a obtained in the step (1) by suction filtration, keeping the filtration state unchanged after the filtration is finished, and washing the residue on the filter membrane by pure water;
(3) Adding the residues obtained in the step (2) and the filter membrane into the aqua regia solution, ultrasonically stripping the residues from the filter membrane, taking out the filter membrane by using tweezers, and washing trace residues adhered to the filter membrane into the aqua regia solution by using deionized water to obtain a mixed solution b of the residues and the aqua regia;
(4) Adding the queen bee water solution into the mixed solution b in the step (3), heating, and evaporating and drying the solution;
(5) Repeating the step (4) once after cooling, and fixing the volume to obtain a solution c after cooling again;
(6) Determination of Co content in solution cAmount (atomic absorption or other common method can be selected for measurement method), and then converted into Co 3 O 4 Value, i.e. LiCo 0.975 Al 0.02 Ti 0.005 O 2 ·rCo 3 O 4 Middle Co 3 O 4 The content of (b).
In this example, co 3 O 4 The content of (A) was measured to be 19917ppm, and r =0.01, i.e. the molecular formula is LiCo 0.975 Al 0.02 Ti 0.005 O 2 ·0.01Co 3 O 4 。
In this embodiment, the preparation method of the positive electrode active material for the lithium ion battery includes the following steps:
(1) According to the formula Li 1.04 Co 0.98 Al 0.02 O 2 Weighing the materials, mixing uniformly, and sintering in a bell jar furnace with air. Wherein, the precursor containing lithium is lithium carbonate, and the precursor containing cobalt is Co with D50 of 17 μm 3 O 4 The precursors containing Al are respectively Al 2 O 3 The sintering temperature is 1050 ℃, the sintering time is 10h, and the whole sintering process is carried out in the air atmosphere. And (3) sieving and crushing the sintered lithium cobaltate to obtain the lithium cobaltate LCO-C.
(2) According to the molecular formula LiCo 0.975 Al 0.02 Ti 0.005 O 2 ·rCo 3 O 4 Mixing LCO-C with varying amounts of Co 3 O 4 Mixing, and adding TiO in an amount of 0.5 mol% 2 And after being uniformly mixed, the mixture is placed into a bell jar furnace which can be ventilated with air to be sintered to obtain the lithium ion battery anode active material. Wherein the sintering temperature is 900 ℃, the sintering time is 10h 3 O 4 D50 of (2) is 3 mu m of agglomerated particles, and D50 of primary particles is less than 1 mu m.
Example 4:
co in lithium ion battery positive active material 3 O 4 The content determination method comprises the following steps:
(1) Adding a certain amount of lithium ion battery positive active material (LiCo molecular formula) 0.97 Al 0.02 Mg 0.005 Ti 0.005 O 2 ·rCo 3 O 4 ) Adding CrCl 2 +CuCl 2 Solution and HCl + H 2 SO 4 Magnetically stirring and dissolving for 1.2h to obtain a solution a;
(2) Filtering the solution a obtained in the step (1) by suction filtration, keeping the filtration state unchanged after the completion of the filtration, and washing the residue on the filtration membrane with pure water;
(3) Adding the residues obtained in the step (2) and the filter membrane into a nitric acid (with the mass concentration of 50%) solution, ultrasonically stripping the residues from the filter membrane, taking out the filter membrane by using tweezers, and washing a trace amount of residues adhered to the filter membrane into the nitric acid solution by using deionized water to obtain a mixed solution b of the residues and the nitric acid;
(4) Adding a nitric acid solution into the mixed solution b in the step (3), heating, and evaporating and drying the solution;
(5) Repeating the step (4) once after cooling, and fixing the volume to obtain a solution c after cooling again;
(6) Measuring the Co content in the solution c (the measuring method may be atomic absorption or other common methods), and converting into Co 3 O 4 Value, i.e. LiCo 0.97 Al 0.02 Mg 0.005 Ti 0.005 O 2 ·0.01Co 3 O 4 Medium Co 3 O 4 The content of (a).
In this example, co 3 O 4 The content of (b) is 20130ppm, and r =0.01 is calculated, namely LiCo is the molecular formula 0.97 Al 0.02 Mg 0.005 Ti 0.005 O 2 ·0.01Co 3 O 4 。
In this embodiment, the preparation method of the positive electrode active material for the lithium ion battery includes the following steps:
(1) According to the formula Li 1.04 Co 0.98 Al 0.02 O 2 Weighing the materials, mixing uniformly, and sintering in a bell jar furnace with air. Wherein, the precursor containing lithium is lithium carbonate, and the precursor containing cobalt is Co with D50 of 17 μm 3 O 4 Precursors containing Al are respectively Al 2 O 3 The sintering temperature is 1050 ℃, the sintering time is 10h, and the whole sintering process is carried out in the air atmosphere. And (3) sieving and crushing the sintered lithium cobaltate to obtain the lithium cobaltate LCO-D.
(2) According to the molecular formula LiCo 0.97 Al 0.02 Mg 0.005 Ti 0.005 O 2 ·rCo 3 O 4 Mixing LCO-D with varying amounts of Co 3 O 4 Mixing, adding 0.5 mol% of MgO and 0.5 mol% of TiO 2 And after being uniformly mixed, the mixture is placed into a bell jar furnace which can be ventilated with air for sintering treatment to obtain the lithium ion battery anode active material. Wherein the sintering temperature is 900 ℃, the sintering time is 10h, and Co 3 O 4 D50 of (2) is 3 mu m of agglomerated particles, and D50 of primary particles is less than 1 mu m.
Claims (7)
1. Co in lithium ion battery positive active material 3 O 4 The content determination method is characterized in that the lithium ion battery positive electrode active material is lithium cobalt metal oxide powder, and the general formula of the lithium cobalt metal oxide powder is Li a Co 1-x- y M x N y O 2 ·r Co 3 O 4 Wherein r is more than 0.002 and less than or equal to 0.05, a is more than or equal to 1 and less than or equal to 1.1, x is more than or equal to 0 and less than or equal to 0.02, y is more than or equal to 0 and less than or equal to 0.005, a is more than or equal to 1+3r, M is a doping element, and N is a coating element; the lithium cobalt metal oxide powder is of a coating structure and comprises a lithium cobalt metal oxide matrix and Co 3 O 4 A coating layer, wherein excessive Co exists in the inner and outer surfaces of the lithium cobalt metal oxide matrix 3 O 4 Co inside the lithium cobalt metal oxide matrix 3 O 4 With Co of the outer surface 3 O 4 Is less than 1, comprising the following steps:
(1) Adding an impregnating agent into a sample to be measured, adding a metal ion salt solution, and fully stirring and dissolving to obtain a solution a;
(2) Filtering the solution a obtained in the step (1), and cleaning residues on a filter membrane after the filtration is finished;
(3) Adding the residues obtained in the step (2) and the filter membrane into a strong acid solution, completely stripping the residues on the filter membrane into the strong acid solution, wherein the strong acid is one or more of nitric acid, hydrochloric acid and aqua regia, and the mass concentration of the nitric acid, the hydrochloric acid and the aqua regia is 30-70%, so as to obtain a mixed solution b of the residues and the strong acid solution;
(4) Adding a strong acid solution into the mixed solution b in the step (3), heating, evaporating and drying;
(5) Cooling and fixing the volume to obtain a solution c;
(6) The content of Co in the solution c was measured and converted to Co 3 O 4 Value, namely obtaining Co in the sample to be measured 3 O 4 The content of (b).
2. Co in the positive active material of the lithium ion battery according to claim 1 3 O 4 The method for measuring the content is characterized in that the step (4) is repeated at least once before the step (5) is carried out.
3. Co in the positive active material of the lithium ion battery according to claim 1 or 2 3 O 4 The content determination method is characterized in that the impregnating agents are HCl and H 2 SO 4 And H 3 PO 4 And at least contains H 2 SO 4 Or H 3 PO 4 One or both of them.
4. Co in the positive active material of the lithium ion battery according to claim 1 or 2 3 O 4 The content determination method is characterized in that the metal ion salt solution is NiSO 4 、NiCl 2 、MnSO 4 、MnCl 2 、FeSO 4 、FeCl 2 、Cu 2 SO 4 、CuCl 2 、CrSO 4 And CrCl 2 One or more of (a).
5. Co in the positive active material for lithium ion battery according to claim 1 or 2 3 O 4 The content determination method is characterized in that in the step (1), the stirring time is 0.5-2 h.
6. Co in the positive active material of the lithium ion battery according to claim 5 3 O 4 The content determination method is characterized in that the stirring time is 0.8-1.4 h.
7. Co in the positive active material of the lithium ion battery according to claim 1 3 O 4 The method for measuring the content is characterized in that M is one or more of Mg, ca, cu, al, B, ti, Y and Zr, and N is one or more of Na, K, mg, ca, cu, al, B, ti, Y, zr, ni and Mn.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710983605.0A CN109696520B (en) | 2017-10-20 | 2017-10-20 | Co in lithium ion battery positive active material 3 O 4 Content determination method |
| KR1020207011291A KR102400050B1 (en) | 2017-10-20 | 2018-04-26 | Lithium cobalt metal oxide powder, method for preparing same, and method for determining content of cobalt (II, III) oxide |
| EP18869182.8A EP3699987A4 (en) | 2017-10-20 | 2018-04-26 | Lithium cobalt metal oxide powder and preparation method therefor, and method for measuring content of tricobalt tetroxide |
| PCT/CN2018/084679 WO2019076023A1 (en) | 2017-10-20 | 2018-04-26 | Lithium cobalt metal oxide powder and preparation method therefor, and method for measuring content of tricobalt tetroxide |
| JP2020521456A JP7034275B2 (en) | 2017-10-20 | 2018-04-26 | Lithium-cobalt metal oxide powder, its preparation method, and method for determining the content of cobalt (II, III). |
| US16/756,889 US11784309B2 (en) | 2017-10-20 | 2018-04-26 | Lithium cobalt metal oxide powder, method for making the same, and method for determining content of cobalt (II,III) oxide |
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