CN108565455A - A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor - Google Patents

A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor Download PDF

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Publication number
CN108565455A
CN108565455A CN201810542026.7A CN201810542026A CN108565455A CN 108565455 A CN108565455 A CN 108565455A CN 201810542026 A CN201810542026 A CN 201810542026A CN 108565455 A CN108565455 A CN 108565455A
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nickel cobalt
cobalt manganese
complexing agent
ternary precursor
salt
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李建刚
姚琼
刘才
王丽媛
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of methods that non-nitrogen containing complexing agent assists preparing spherical nickel cobalt manganese ternary precursor, including:Nickel salt, cobalt salt, manganese salt are configured to the nickel cobalt manganese mixing salt solution that metal ion total concentration is 1.0~2.0mol/L;The nickel cobalt manganese mixing salt solution, sodium hydroxide solution, non-nitrogen containing complexing agent are added into reaction kettle simultaneously, and under the conditions of protecting gas shielded, controlling reaction temperature is 53~57 DEG C, and the pH value for controlling mixture in reaction kettle maintains 10.9~11.1;After these three solution persistently add 6 hours, stops liquid feeding, and be aged 10 hours, then be separated by solid-liquid separation, obtain spherical nickel cobalt manganese ternary precursor Ni1‑x‑yCoxMny(OH)2.The high spherical nickel cobalt manganese ternary precursor of compactness can not only be made in the present invention, and used complexing agent is not tasteless, nontoxic, nitrogenous, can improve production environment, mitigate the pollution processing load in production waste water.

Description

A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor
Technical field
The present invention relates to lithium ion battery electrode material preparing technical fields more particularly to a kind of non-nitrogen containing complexing agent to assist The method for preparing spherical nickel cobalt manganese ternary precursor.
Background technology
Anode material for lithium-ion batteries is one of four important components of lithium ion battery, to the electrification of lithium ion battery Performance and security performance play the role of vital.With the fast development of electric vehicle, to lithium ion battery correlation Electrode material proposes higher performance requirement.Due to nickle cobalt lithium manganate (LiNi1-x-yCoxMnyO2) ternary material have Gao Rong The advantages that amount, long circulation life, and the ratio that nickel, three kinds of cobalt, manganese elements is adjusted flexibly can be needed according to application, therefore should Material has become the main product of current electronic automobile-used power lithium-ion battery positive electrode.
Currently, cobalt nickel lithium manganate ternary material in the market mainly has LiNi1/3Co1/3Mn1/3O2(111)、 LiNi0.4Co0.2Mn0.4O2(424)、LiNi0.5Co0.2Mn0.3O2(523) and LiNi0.6Mn0.2Co0.2O2(622), these material bases This is all by spherical nickel cobalt manganese ternary precursor Ni1-x-yCoxMny(OH)2It is prepared through high-temperature calcination after being mixed with lithium salts. And spherical nickel cobalt manganese ternary precursor Ni1-x-yCoxMny(OH)2Preparation method be all and to be adopted using control crystallisation It is complexing agent with ammonium hydroxide, such as:The Chinese patents such as CN105731553A, CN106684351A, CN106920934A are to use This method;Not only ammonium hydroxide smell is big for this method, and production environment is bad, and produces ammonia-nitrogen content height, control expense in waste water Greatly, therefore it is badly in need of developing a kind of preparation method without spherical nickel cobalt manganese ternary precursor of the ammonium hydroxide as complexing agent.
In the prior art,《The research of lithium ion battery new electrode materials》(Wang Chuanbao, Nanjing Aero-Space University, 2012) it proposes and a kind of the side of spherical nickel cobalt manganese ternary precursor is prepared as complexing agent using EDTA (ethylenediamine tetra-acetic acid) The higher spherical nickel cobalt manganese ternary precursor of compactness can be successfully made, since EDTA does not have smell, production environment in method Very big improvement has been obtained, but has still contained nitrogen in EDTA, the ammonia-nitrogen content produced in waste water is still higher, waste water treatment The big puzzlement of difficulty does not solve still.
Invention content
For above-mentioned shortcoming in the prior art, the present invention provides a kind of non-nitrogen containing complexing agents to assist preparing spherical shape The method of nickel-cobalt-manganese ternary presoma can not only be made the high spherical nickel cobalt manganese ternary precursor of compactness, and be used Complexing agent is not tasteless, nontoxic, nitrogenous, can improve production environment, mitigates the pollution processing load in production waste water.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor, includes the following steps:
Step A, according to nickel salt:Cobalt salt:Manganese salt=1:1:1 or 4:2:4 or 5:2:3 or 6:2:2 or 8:1:1 molar ratio, Nickel salt, cobalt salt, manganese salt are configured to the nickel cobalt manganese mixing salt solution that metal ion total concentration is 1.0~2.0mol/L;
Step B, under agitation, by the nickel cobalt manganese mixing salt solution, the hydroxide of a concentration of 1.0~4.0mol/L Sodium solution, a concentration of 0.2~0.8mol/L non-nitrogen containing complexing agent simultaneously added into reaction kettle, and protection gas shielded condition Under, controlling reaction temperature is 53~57 DEG C, while adjusting the addition of sodium hydroxide solution, makes the pH value of mixture in reaction kettle Maintain 10.9~11.1;After these three solution persistently add 6 hours, stop liquid feeding, and be aged 10 hours, then carry out solid-liquid Separation, to which spherical nickel cobalt manganese ternary precursor Ni be made1-x-yCoxMny(OH)2
Preferably, the non-nitrogen containing complexing agent is at least one of sodium gluconate, sodium citrate.
Preferably, the protection gas uses at least one of nitrogen or inert gas.
Preferably, in stepb, it is washed and is dried successively after separation of solid and liquid.
A kind of spherical nickel cobalt manganese ternary precursor prepares spherical nickel cobalt manganese ternary using above-mentioned non-nitrogen containing complexing agent auxiliary The method of presoma is prepared.
As seen from the above technical solution provided by the invention, non-nitrogen containing complexing agent auxiliary provided by the invention prepares ball The method of shape nickel-cobalt-manganese ternary presoma is in protection compression ring border, by nickel cobalt manganese mixing salt solution, the hydroxide of specific proportioning Sodium solution, non-nitrogen containing enveloping agent solution are added into reaction kettle simultaneously, and by controlling stirring intensity, reaction temperature, reaction kettle Interior mixture ph is reacted, aged after reaction and separation of solid and liquid, to can be obtained particle good sphericity, jolt ramming The high spherical nickel cobalt manganese ternary precursor Ni of density1-x-yCoxMny(OH)2.The present invention provides a kind of non-nitrogen containing complexing agent auxiliary It is tasteless, nontoxic, not nitrogenous to prepare complexing agent used in the method for spherical nickel cobalt manganese ternary precursor, production ring can be improved Border mitigates the pollution processing load in production waste water, and control crystallisation process route phase is complexed with ammonium hydroxide in the prior art Seemingly, upgrading, which substitutes, is easy, without increasing extras.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this For the those of ordinary skill in field, without creative efforts, other are can also be obtained according to these attached drawings Attached drawing.
Fig. 1 is spherical nickel cobalt manganese ternary precursor Ni in the embodiment of the present invention 10.6Co0.2Mn0.2(OH)2Scanning electron microscope shine Piece.
Fig. 2 is nickel-cobalt-manganternary ternary anode material LiNi in the embodiment of the present invention 10.6Co0.2Mn0.2O2Stereoscan photograph.
Fig. 3 is nickel-cobalt-manganternary ternary anode material LiNi in the embodiment of the present invention 10.6Co0.2Mn0.2O2First run charge and discharge it is bent Line.
Specific implementation mode
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete Ground describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts Example, belongs to protection scope of the present invention.
Below to non-nitrogen containing complexing agent provided by the present invention assist prepare spherical nickel cobalt manganese ternary precursor method into Row detailed description.The content not being described in detail in the present invention belongs to the prior art well known to professional and technical personnel in the field.
A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor, includes the following steps:
Step A, according to nickel salt:Cobalt salt:Manganese salt=1:1:1 or 4:2:4 or 5:2:3 or 6:2:2 or 8:1:1 molar ratio, Nickel salt, cobalt salt, manganese salt are configured to the nickel cobalt manganese mixing salt solution that metal ion total concentration is 1.0~2.0mol/L.
Step B, in high-speed stirred, (high-speed stirred refers to that agitating paddle is stirred with the rotating speed of 500~1500r/min Mix) under the conditions of, by the nickel cobalt manganese mixing salt solution, the sodium hydroxide solution of a concentration of 1.0~4.0mol/L, a concentration of 0.2 These three solution of the non-nitrogen containing complexing agent of~0.8mol/L are added into reaction kettle simultaneously, and under the conditions of protecting gas shielded, control Reaction temperature processed is 53~57 DEG C, while adjusting the addition of sodium hydroxide solution, and the pH value of mixture in reaction kettle is made to maintain 10.9~11.1, after these three solution persistently add 6 hours, stop liquid feeding, continues stirring ageing 10 hours, then consolidated Liquid separation, washing and drying, to which spherical nickel cobalt manganese ternary precursor Ni be made1-x-yCoxMny(OH)2
Wherein, the non-nitrogen containing complexing agent is at least one of sodium gluconate, sodium citrate;The protection gas can be adopted With at least one of nitrogen or inert gas;Filtering or suction filtration can be used in the separation of solid and liquid;The washing can be used Pure water is washed.
Compared with prior art, non-nitrogen containing complexing agent auxiliary provided by the present invention prepares spherical nickel cobalt manganese ternary precursor Method at least have the advantages that:
(1) made in the method for non-nitrogen containing complexing agent auxiliary preparation spherical nickel cobalt manganese ternary precursor provided by the present invention It is tasteless, nontoxic, not nitrogenous with complexing agent, production environment can be improved, mitigate the pollution processing load in production waste water.
(2) non-nitrogen containing complexing agent provided by the present invention auxiliary prepare the method for spherical nickel cobalt manganese ternary precursor with it is existing Ammonium hydroxide complexing control crystallisation process route is similar in technology, and upgrading, which substitutes, to be easy, without increasing extras.
(3) non-nitrogen containing complexing agent auxiliary provided by the present invention prepares the method and process letter of spherical nickel cobalt manganese ternary precursor It is single, it is very suitable for a large amount of, the continuous production of industry.
(4) method that non-nitrogen containing complexing agent auxiliary provided by the present invention prepares spherical nickel cobalt manganese ternary precursor, system For the spherical nickel cobalt manganese ternary precursor Ni gone out1-x-yCoxMny(OH)2Particle good sphericity, tap density can reach 2.4g/cm3, It can be used for preparing the nickel-cobalt-manganternary ternary anode material LiNi of excellent electrical property1-x-yCoxMnyO2, therefore can be widely applied to high specific energy Secondary cell field.
To sum up, the high spherical nickel cobalt manganese ternary precursor of compactness, Er Qiesuo can not only be made in the embodiment of the present invention It is tasteless using complexing agent, nontoxic, not nitrogenous, production environment can be improved, mitigate the pollution processing load in production waste water.
In order to more clearly from show technical solution provided by the present invention and generated technique effect, below with tool The method that body embodiment prepares spherical nickel cobalt manganese ternary precursor to the non-nitrogen containing complexing agent auxiliary of the present invention is described in detail.
Embodiment 1
A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor, includes the following steps:
Step a1, according to nickel salt:Cobalt salt:Manganese salt=6:2:2 molar ratio, by nickel salt, cobalt salt, manganese salt be configured to metal from The nickel cobalt manganese mixing salt solution of a concentration of 2.0mol/L of subpopulation.
Step b1, under the conditions of the high-speed stirred that low whipping speed is 600r/min, using metering pump respectively by the nickel cobalt The sodium citrate solution of manganese mixing salt solution, the sodium hydroxide solution of a concentration of 2.0mol/L and a concentration of 0.5mol/L simultaneously to It is pumped into sealing reaction kettle, and under the conditions of nitrogen protection, controlling reaction temperature is 53~57 DEG C, while it is molten to adjust sodium hydroxide The addition of liquid makes the pH value of mixture in reaction kettle maintain 10.9~11.1;Wait for that these three solution average rates are pumped into 6 hours Afterwards, stop liquid feeding, and continue stirring ageing 10 hours, then take out reaction solution from reaction kettle, filtered, washed and done successively It is dry, to which fully dry spherical nickel-cobalt spherical nickel cobalt manganese ternary precursor Ni as shown in Figure 1 be made0.6Co0.2Mn0.2 (OH)2
Specifically, by spherical nickel-cobalt spherical nickel cobalt manganese ternary precursor fully dry obtained by the embodiment of the present invention 1 Ni0.6Co0.2Mn0.2(OH)2It is sufficiently mixed with lithium carbonate, makes Li:(Ni+Co+Mn)=1.08 it (is calculated according to molar ratio), Then it is calcined in Muffle furnace, rises to 550 DEG C with the heating rate of 5 DEG C/min, keep the temperature 5h, then with the heating rate of 5 DEG C/min 850 DEG C are warming up to, 12h is kept the temperature, is then naturally cooling to room temperature, and roasted, be ground up, sieved, to obtain as shown in Figure 2 Nickel-cobalt-manganternary ternary anode material LiNi0.6Co0.2Mn0.2O2
Further, to the nickel-cobalt-manganternary ternary anode material LiNi obtained by the embodiment of the present invention 10.6Co0.2Mn0.2O2Into Row charge and discharge electro-detection, so as to obtain first run charging and discharging curve as shown in Figure 3.It can be seen that by Fig. 1, Fig. 2 and Fig. 3:This Spherical nickel-cobalt spherical nickel cobalt manganese ternary precursor Ni obtained by inventive embodiments 10.6Co0.2Mn0.2(OH)2Good sphericity, jolt ramming Density is up to 2.4g/cm3, at room temperature when 0.2C charge and discharge, specific discharge capacity reaches 172mAh/g or more.
Embodiment 2
A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor, includes the following steps:
Step a2, according to nickel salt:Cobalt salt:Manganese salt=6:2:2 molar ratio, by nickel salt, cobalt salt, manganese salt be configured to metal from The nickel cobalt manganese mixing salt solution of a concentration of 2.0mol/L of subpopulation.
Step b2, under the conditions of the high-speed stirred that low whipping speed is 600r/min, using metering pump respectively by the nickel cobalt Manganese mixing salt solution, the sodium hydroxide solution of a concentration of 2.0mol/L, a concentration of 0.8mol/L sodium gluconate solution simultaneously It is pumped into sealing reaction kettle, and under the conditions of nitrogen protection, controlling reaction temperature is 53~57 DEG C, while adjusting sodium hydroxide The addition of solution makes the pH value of mixture in reaction kettle maintain 10.9~11.1;Wait for that these three solution average rates are pumped into 6 hours Afterwards, stop liquid feeding, and continue stirring ageing 10 hours, then take out reaction solution from reaction kettle, filtered, washed and done successively It is dry, to which fully dry spherical nickel-cobalt spherical nickel cobalt manganese ternary precursor Ni be made0.6Co0.2Mn0.2(OH)2
Specifically, by spherical nickel-cobalt spherical nickel cobalt manganese ternary precursor fully dry obtained by the embodiment of the present invention 2 Ni0.6Co0.2Mn0.2(OH)2It is sufficiently mixed with lithium carbonate, makes Li:(Ni+Co+Mn)=1.08 it (is calculated according to molar ratio), Then it is calcined in Muffle furnace, rises to 550 DEG C with the heating rate of 5 DEG C/min, keep the temperature 5h, then with the heating rate of 5 DEG C/min 850 DEG C are warming up to, 12h is kept the temperature, room temperature is then naturally cooling to, and roasted, be ground up, sieved, to obtain nickel cobalt manganese three First positive electrode LiNi0.6Co0.2Mn0.2O2.Spherical nickel-cobalt spherical nickel cobalt manganese ternary precursor obtained by the embodiment of the present invention 2 Ni0.6Co0.2Mn0.2(OH)2Good sphericity, tap density is up to 2.4g/cm3, at room temperature when 0.2C charge and discharge, specific discharge capacity reaches To 170mAh/g or more.
To sum up, the high spherical nickel cobalt manganese ternary precursor of compactness, Er Qiesuo can not only be made in the embodiment of the present invention It is tasteless using complexing agent, nontoxic, not nitrogenous, production environment can be improved, mitigate the pollution processing load in production waste water.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in, It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims Subject to enclosing.

Claims (5)

1. a kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor, which is characterized in that including following Step:
Step A, according to nickel salt:Cobalt salt:Manganese salt=1:1:1 or 4:2:4 or 5:2:3 or 6:2:2 or 8:1:1 molar ratio, by nickel Salt, cobalt salt, manganese salt are configured to the nickel cobalt manganese mixing salt solution that metal ion total concentration is 1.0~2.0mol/L;
Step B, under agitation, the nickel cobalt manganese mixing salt solution, the sodium hydroxide of a concentration of 1.0~4.0mol/L is molten Liquid, a concentration of 0.2~0.8mol/L non-nitrogen containing complexing agent added simultaneously into reaction kettle, and under the conditions of protecting gas shielded, Controlling reaction temperature is 53~57 DEG C, while adjusting the addition of sodium hydroxide solution, and the pH value of mixture in reaction kettle is made to tie up It holds 10.9~11.1;After these three solution persistently add 6 hours, stop liquid feeding, and be aged 10 hours, then carry out solid-liquid point From to which spherical nickel cobalt manganese ternary precursor Ni be made1-x-yCoxMny(OH)2
2. the method that non-nitrogen containing complexing agent auxiliary according to claim 1 prepares spherical nickel cobalt manganese ternary precursor, special Sign is that the non-nitrogen containing complexing agent is at least one of sodium gluconate, sodium citrate.
3. the method that non-nitrogen containing complexing agent auxiliary according to claim 1 or 2 prepares spherical nickel cobalt manganese ternary precursor, It is characterized in that, the protection gas uses at least one of nitrogen or inert gas.
4. the method that non-nitrogen containing complexing agent auxiliary according to claim 1 or 2 prepares spherical nickel cobalt manganese ternary precursor, It is characterized in that, in stepb, is washed and dried successively after separation of solid and liquid.
5. a kind of spherical nickel cobalt manganese ternary precursor, which is characterized in that described in any one of the claims 1 to 4 The method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor is prepared.
CN201810542026.7A 2018-05-30 2018-05-30 A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor Pending CN108565455A (en)

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CN112794376A (en) * 2021-01-20 2021-05-14 湖南德景源科技有限公司 Preparation method of nickel-cobalt-manganese ternary material precursor
CN114639820A (en) * 2022-03-10 2022-06-17 陕西沣锡致远新材料科技有限公司 Preparation method of spherical glucose nickel-cobalt-manganese complex and application of spherical glucose nickel-cobalt-manganese complex to secondary battery
CN115490274A (en) * 2022-08-22 2022-12-20 西南交通大学 Preparation method of LiNi0.6Co0.2Mn0.2O2 and electrochemical performance test method thereof
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Publication number Priority date Publication date Assignee Title
CN112794376A (en) * 2021-01-20 2021-05-14 湖南德景源科技有限公司 Preparation method of nickel-cobalt-manganese ternary material precursor
CN115924986A (en) * 2021-10-19 2023-04-07 浙江海创锂电科技有限公司 Preparation method of high-nickel ternary precursor material
CN114639820A (en) * 2022-03-10 2022-06-17 陕西沣锡致远新材料科技有限公司 Preparation method of spherical glucose nickel-cobalt-manganese complex and application of spherical glucose nickel-cobalt-manganese complex to secondary battery
CN114639820B (en) * 2022-03-10 2024-02-27 陕西沣锡致远新材料科技有限公司 Preparation method of spherical glucose nickel cobalt manganese complex and application of spherical glucose nickel cobalt manganese complex in secondary battery
CN115490274A (en) * 2022-08-22 2022-12-20 西南交通大学 Preparation method of LiNi0.6Co0.2Mn0.2O2 and electrochemical performance test method thereof

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Application publication date: 20180921