CN106159254B - Nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor preparation method - Google Patents
Nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor preparation method Download PDFInfo
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- CN106159254B CN106159254B CN201510197027.9A CN201510197027A CN106159254B CN 106159254 B CN106159254 B CN 106159254B CN 201510197027 A CN201510197027 A CN 201510197027A CN 106159254 B CN106159254 B CN 106159254B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection 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
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Abstract
The invention belongs to electrode material preparation fields, and in particular to the preparation method of a kind of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor.The metal salt solution being configured to, precipitating reagent and template mixed solution, template solution are carried out liquid-liquid coprecipitation reaction by this method in reaction, obtain sediment；Processing, cleaning treatment, vacuum drying treatment are filtered to sediment again, obtain the presoma.Flaky nanometer structure of the invention has many advantages, such as that large specific surface area, reactivity are high；The nanometer sheet presoma ternary obtained or rich lithium manganese base solid solution positive electrode electrochemical performance.Preparation method simple process of the invention, environmental-friendly, energy-efficient, product quality is uniform, reproducible, and gained nanometer sheet is easily dispersed, and is produced on a large scale.
Description
Technical field
The invention belongs to electrode material preparation fields, and in particular to nano-sheet ternary or rich lithium manganese base solid solution anode material
The preparation method of material precursor.
Background technique
Tertiary cathode material is also referred to as nickle cobalt lithium manganate, and chemical formula can be written as Li (NixCoyMnz)O2(x+y+z=1),
Nickel cobalt manganese ratio in ternary composite cathode material can adjust according to actual needs.Ternary material does the anode of lithium ion battery
For cobalt acid lithium material have safety it is good, it is low in cost, gram volume height (> 150mAh/g), operating voltage with it is existing
Electrolyte matches the advantages that (4.1V), the disadvantage is that discharge platform is lower with respect to cobalt acid lithium and LiMn2O4.Comprehensively consider above-mentioned excellent scarce
The features such as point and its compacted density are high, ternary material are at present using the maximum positive electrode of best and yield.
Rich lithium manganese base solid solution positive electrode has layer structure, and chemical formula can be written as xLi2MnO3·(1-x)LiMO2
(wherein M is transition metal, 0 < x < 1), theoretical specific capacity is more than 300mAh/g, and actually available capacity is also greater than 250mAh/g,
It is 2 times or so of presently used positive electrode actual capacity.In addition, due to largely making in the rich lithium manganese base solid solution positive electrode
With Mn element, also have that at low cost, safety is good, advantages of environment protection compared with cobalt acid lithium and ternary material.Therefore rich lithium
Manganese-based anode material is considered as the ideal chose of next-generation anode material for lithium-ion batteries.
However either above-mentioned tertiary cathode material or rich lithium manganese base solid solution positive electrode, to give full play to
The performance of material improves the high rate performance of material, it is still necessary to advanced optimize technique in the synthesis of material, for example prepare nanometer
The ternary or lithium-rich manganese-based anode material of scale.Solve to prepare the ternary or rich lithium manganese base solid solution material of Nano grade, most
Easy way is exactly the persursor material that preparation has nanostructure.If obtaining nano-sheet with a kind of technique easy to accomplish
Persursor material, then pass through technology controlling and process in the later sintering process, it may be convenient to synthesize the ternary of Nano grade
Or stratiform rich lithium manganese base solid solution material.
Template is a kind of method of very useful preparation nano material, and prepared material has a variety of nanometers of shapes
Looks, such as nanosphere, nanometer rods, nanometer sheet etc..The precursor synthesis of ternary or rich lithium manganese carries out in the liquid phase at present,
It is very convenient in conjunction with template.Thus, the ternary of nanometer or the forerunner of rich lithium manganese base solid solution are prepared by means of template
Body, and then prepare corresponding nano material and be very effective the means for improving material property, to preferably play material
Chemical property.
In the prior art, ternary or the precursor synthesis method advantage and disadvantage that are very much, but having nothing in common with each other of rich lithium manganese:
(1) Zhi Xiao section, Liu Hongguang et al. have invented a kind of preparation method of lithium ion battery lithium-rich manganese-based anode material,
This method is carbonized by adding starch during precursor synthesis, and then in the sintering process in later period, improves leading for material
Electrical property.But material is not carried out nanosizing processing by this method, so the true capacity of material is difficult to give full play of (most
Dawn section, Liu Hongguang, the leaf sea of learning, He Aizhen, Zhang Su, Shi Jie, rising sun sun, a kind of system of lithium ion battery lithium-rich manganese-based anode material
Preparation Method, Chinese invention patent application, application number: 201210357169.3, the applying date: 2012-09-21, publication No.: CN
102881887A)。
(2) Wu Feng, old reality et al. have invented a kind of preparation method of lithium-rich manganese-based ternary composite cathode material, and this method is logical
The mode for crossing control co-precipitation obtains presoma, and the particle size distribution of gained persursor material is uniform, and the performance of material obtains
Optimization, but process conditions required by this method are complicated, it is difficult to the control (Wu of realization grain graininess in the industrial production
Cutting edge of a knife or a sword, Chen Shi, Zhong Yunxia, Bai Ying, Wuchuan, Bao Liying, Wu Bairong, a kind of preparation side of lithium-rich manganese-based ternary composite cathode material
Method, Chinese invention patent application, application number: 201210149592.4, the applying date: 2012-05-14, publication No.:
CN102655232A)。
(3) Hou Hongjun, Li Shijiang et al. have invented a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode and its preparation
Method, this method obtain the rich lithium manganese solid solution material of doping and spherical shape, the performance of material by the modes such as adulterating, being spray-dried
Preferably, but the technique of spray drying used in this method is difficult to amplify, and is equally to be difficult to large batch of system in the industrial production
Standby spherical rich lithium manganese solid solution material (Hou Hongjun, Li Shijiang, Luo Chengguo, Luo Chuanjun, Yang Huachun, Li Yunfeng, Xue Xujin, Ding Yun
The tinkling of pieces of jade, Zhao Yongfeng, a kind of microballoon stratiform rich lithium manganese base solid solution positive electrode and preparation method thereof, Chinese invention patent application, Shen
Please number: 201210435110.1, applying date: 2012-11-02, publication No.: CN102916176A).
(4) the Chinese patent application preparation method of high-capacity lithium ion cell tertiary cathode material " long-life, " (application
Number: 201310711940.7, publication No. CN103682316A) in, lithium salts is normally sintered by Wang Zhenbo et al. with presoma
Then synthesis of ternary material carries out twice lithium adding and TiO2It carries out secondary clacining and obtains tertiary cathode material.But the preparation side
Secondary clacining will increase energy consumption in method, and the secondary lithium salts that increases will increase the preparation cost of material.
(5) Chinese patent application " a kind of composite multi-component anode material for lithium-ion batteries and preparation method thereof " (application number:
201410181128.2, publication No. CN103928673A) in, Ernest & Whitney Science and Technology Ltd. is matched with nickle cobalt lithium manganate anode in Chengdu
Material is core, coats the oxide of one layer of transition metal (or nonmetallic) and lithium with similar structure, and then formed by interior
Outside gradient doping, but gradient doping way used by the preparation method can greatly increase the difficulty of production technology
Degree, gradient and the uniformity for controlling material granule are very difficult.
(6) Chinese patent application " a kind of composite material and preparation method " (application number: 201410457559.7, announce
Number CN103928673A) in, Hong Kong Applied Science and Technology Research Institute Company Limited uses the polyelectrolyte and transition metal of cationic
It carries out compound, then obtains can be applied to the compound group that the laminar nano thin slice of lithium-rich anode material is constituted in hydrothermal reaction kettle
Cluster.But hydrothermal reaction kettle used by the preparation method needs high temperature, high pressure and longer preparation time, this can be in very great Cheng
Its production scale in practical applications is limited on degree.
Preparation in scientific and technical literature about rich lithium manganese also has very much:
(1) Na ion exchange is Li ion from the material accordingly containing Na with ion-exchange by Kim et al., and then is obtained
Obtained rich lithium manganese solid solution material.The high rate performance of the material is preferable, but the institute of ion-exchange process used in this method having time
It is longer, and yield very limited (Kim D, Kang SH, Balasubramanian M, Johnson CS, High-energy
and high-power Li-rich nickel manganese oxide electrode
materials.Electrochemistry Communications,2010,12,1618–1621)。
(2) domestic Sun Shigang seminar obtains the lithium-rich manganese-based solid solution of crystal grain oriented growth by hydro-thermal reaction
Body material, the material also have an excellent high rate performance, but hydro-thermal reaction need high temperature and high pressure condition (Wei GZ, Lu X,
Ke FS,Huang L,Li JT,Wang ZX,Zhou ZY,Sun ZG,Crystal Habit-Tuned Nanoplate
Material of Li[Li1/3–2x/3NixMn2/3–x/3]O 2for High-Rate Performance Lithium-
Ion Batteries,Adv.Mater.2010,4364,22,4364-4367)。
(3) MnCO of Huang Yun brightness seminar synthesizing spherical first3Presoma, then by MnCO3, LiOH and Ni (NO3)2It is mixed
It closes sintering and obtains hollow ball shape richness lithium manganese material, material specific capacity with higher and high rate performance, but synthesis used walks
It is rapid more, and the hollow ball structure of material is sintered and required to keep under hot conditions, required process conditions are harsh
(Jiang Y,Yang Z,Luo W,Hu X,Huang Yunhui,Hollow 0.3Li2MnO3_
0.7LiNi0.5Mn0.5O2microspheres as a high-performance cathode material for
lithium–ion batteries,Phys.Chem.Chem.Phys.,2013,15,2954—2960)。
In conclusion different seminar's method therefors of the prior art are different, but all there is some be difficult in industry life
In production the problem of large batch of preparation.Therefore, in current research and production, it is good to be required to a kind of chemical property, can be with
The nano-sheet ternary of large-scale production or the preparation method of rich lithium manganese base solid solution positive electrode material precursor.
Summary of the invention
The present invention provides the preparation method of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor, this method
Include the steps that are as follows: metal salt solution preparation, precipitating reagent and template solution preparation, precursor preparation；It is prepared using the present invention
The obtained positive electrode of precursor preparation have preferable chemical property.
The present invention is achieved by the following technical solutions:
A kind of preparation method of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor, it is characterised in that:
This method comprises the following steps:
Metal salt solution preparation step: manganese salt, cobalt salt and nickel salt are mixed with water, and dissolution obtains metal salt solution；
Precipitating reagent and template mixed solution preparation step: the dissolution soluble in water of precipitating reagent, template is taken, precipitating reagent is obtained
With template mixed solution；
Precursor preparation step: the concentration of first compound concentration and the precipitating reagent and the template in template mixed solution
Identical template solution, is placed in reactor, then by the metal salt solution, precipitating reagent and template mixed solution, template
Agent solution, which is pumped into reactor, carries out liquid-liquid coprecipitation reaction, obtains sediment；Processing is filtered to the sediment again,
Obtain filtered sediment；The filtered sediment is started the cleaning processing again, vacuum drying treatment, obtain it is described before
Drive body.
In above-mentioned preparation method preferred embodiment, the metal salt solution preparation step and precipitant solution preparation
In step, the water is the water that deionized water or purity reach deionized water purity or more.
In above-mentioned preparation method preferred embodiment, in metal salt solution preparation step,
The manganese salt are as follows: one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate are a variety of；
The nickel salt are as follows: one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate are a variety of；
The cobalt salt are as follows: one of cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate are a variety of.
In above-mentioned preparation method preferred embodiment, the metal salt solution of the metal salt solution preparation step
In, metal cation concentration is 0.01mol/L~2.0mol/L.
In above-mentioned preparation method preferred embodiment, in the precipitating reagent and template mixed solution preparation step,
The precipitating reagent is one of lithium hydroxide, ammonium hydrogen carbonate or ammonium carbonate or a variety of, and the concentration of the precipitating reagent is
0.0105mol/L~2.1mol/L；
In above-mentioned preparation method preferred embodiment, in the precipitating reagent and template mixed solution preparation step,
The template is polyvinylpyrrolidone, dodecane sulfonate, cetyl trimethylammonium bromide, myristyl phosphoric acid
One of salt, polyester polyol, hydroxyethyl piperazine second thiosulfonic acid are a variety of；The concentration of the template be 0.001~
0.5mol/L。
In above-mentioned preparation method preferred embodiment, the liquid-liquid co-precipitation of the precursor preparation step is anti-
Ying Zhong, temperature are 20-60 DEG C；The pH value of reaction system is 7-12；The liquid-liquid coprecipitation reaction under inert atmosphere protection into
Row；Preferably, the inert atmosphere is N2 atmosphere or Ar atmosphere.
In above-mentioned preparation method preferred embodiment, in the vacuum drying treatment of the precursor preparation step, temperature
Degree is 80~110 DEG C, and vacuum degree is less than or equal to 10.0Pa, and the time is 2~6 hours.
In above-mentioned preparation method preferred embodiment, the presoma is nanometer sheet；The nanometer sheet with a thickness of 5
~50nm, the nanometer sheet diameter are 50~500nm.
Compared with prior art, the invention has the following beneficial effects:
1, a kind of nano-sheet ternary provided by the invention, the preparation method of rich lithium manganese base solid solution presoma, using mould
Plate agent assembling-coprecipitation prepares nano-sheet presoma, and thickness is in 5-50nm, diameter 50-500nm；Utilize template group
Dress assembles the template of slabbing first in the solution, then the metal salt under the limitation of template in reactor and precipitating reagent into
Row chemical reaction, to obtain the carbonate substance or hydroxide species nano-sheet presoma precipitating of the metal；Utilize mould
Plate agent is self-assembled into sheet soft template, and the precipitating of presoma obtained by chemical coprecipitation reacts on the basis of this template, which is also formed, to be received
Rice laminated structure, the flaky nanometer structure have many advantages, such as that large specific surface area, reactivity are high.With traditional chemical coprecipitation
It compares, the nanometer sheet presoma ternary obtained or rich lithium manganese base solid solution positive electrode electrochemical performance.
2, the presoma nanometer sheet prepared by the present invention can reduce convenient for the infiltration and reaction of lithium salts in later period sintering process
The high temperature sintering time, be sintered 8-10 hours can be obtained finished product in a preferred embodiment, to reduce energy consumption.
3, the nano-sheet presoma prepared by the present invention can be sintered the ternary for preparing Nano grade or lithium-rich manganese-based
Solid solution cathode material, and prepared positive electrode has preferable chemical property, and high rate performance significantly improves.
4, the presoma prepared by the present invention is nanometer sheet, with a thickness of 5-50nm, diameter 50-500nm, has and compares table greatly
Area；With rich lithium manganese base solid solution positive electrode synthesized by this presoma nanometer sheet, discharge capacity is 270-285mAh/ for the first time
G, the special capacity fade very little of material after 30 charge and discharge have preferable cyclical stability；Therefore, forerunner of the invention is utilized
The rich lithium manganese base solid solution positive electrode that body obtains has high stability, high capacity, high conductivity, can be used for high-performance lithium ion
The preparation of battery electrode positive electrode.
5, preparation method simple process provided by the present invention, environmental-friendly, energy-efficient, product quality is uniform, repeats
Property is good, and gained nanometer sheet is easily dispersed, and is produced on a large scale.
Detailed description of the invention
Fig. 1 is the scanning electron microscope for the rich lithium manganese base solid solution positive electrode material precursor that embodiment 1 is prepared
(SEM) picture.
Fig. 2 is the SEM picture for the rich lithium manganese base solid solution positive electrode that embodiment 1 is prepared.
Fig. 3 is X-ray diffraction (XRD) figure for the rich lithium manganese base solid solution positive electrode that embodiment 1 is prepared.
Fig. 4 is the lithium ion two of the rich lithium manganese base solid solution positive electrode that is prepared using embodiment 1 as positive electrode
The first charge-discharge curve graph of primary cell.
Fig. 5 is the lithium ion two of the rich lithium manganese base solid solution positive electrode that is prepared using embodiment 1 as positive electrode
The charge and discharge cycles curve graph of primary cell.
Fig. 6 is the SEM picture for the ternary anode material precursor that embodiment 2 is prepared.
Specific embodiment
The preparation method of a kind of nano-sheet ternary or rich lithium manganese base solid solution positive electrode, includes the following steps:
Step 1: prepared by metal salt solution: manganese salt, cobalt salt and nickel salt being mixed with water, dissolution obtains metal salt solution.
Above-mentioned rapid manganese salt are as follows: one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate are a variety of；
Above-mentioned nickel salt are as follows: one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate are a variety of；
Above-mentioned cobalt salt are as follows: one of cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate are a variety of；
In the metal salt solution, metal cation includes manganese ion, nickel ion, cobalt ions, total concentration 0.01mol/L-
2.0mol/L (illustratively, can for 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L,
It is any or any in 0.5mol/L, 0.6mol/L, 1.0mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L etc.
Range between the two)；
Step 2: precipitating reagent and the preparation of template mixed solution: taking precipitating reagent soluble in water, template stirring is added, obtains
To precipitating reagent and template mixed solution.
In precipitating reagent and template mixed solution preparation step, precipitating reagent is in lithium hydroxide, ammonium hydrogen carbonate or ammonium carbonate
It is one or more, the concentration of precipitating reagent be 0.0105mol/L-2.1mol/L (illustratively, can be 0.0105mol/L,
0.02mol/L、0.05mol/L、0.1mol/L、0.5mol/L、0.6mol/L、0.8mol/L、1.0mol/L、1.2mol/L、
Any or any range between the two in 1.5mol/L, 1.8mol/L, 2.0mol/L, 2.1mol/L etc.)；
Template is polyvinylpyrrolidone, dodecane sulfonate, cetyl trimethylammonium bromide, myristyl phosphorus
One of hydrochlorate, polyester polyol, hydroxyethyl piperazine second thiosulfonic acid are a variety of, and the concentration of template is 0.001-0.5mol/L
(illustratively, can for 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.1mol/L,
Any or any the two in 0.125mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L etc.
Between range)；
The water selected in step 1 and two is that deionized water or purity reach the water of the purity of deionized water or more (as surpassed
Pure water).
Step 3: precursor preparation:
First prepare template identical with the concentration of template in the precipitating reagent and template mixed solution in step 2
Solution, then template solution 40-500ml is added in reactor, then above-mentioned metal salt solution, precipitating reagent and template are mixed
The volume ratio that solution presses 1:1 is closed, is pumped into reactor and carries out liquid-liquid coprecipitation reaction, obtain sediment；
The above-mentioned speed being pumped into reactor is that 5ml/min~30ml/min (illustratively, can be 5ml/min, 7ml/
In min, 8ml/min, 9ml/min, 22ml/min, 24ml/min, 25ml/min, 26ml/min, 28ml/min, 30ml/min etc.
Any or any range between the two),
It (illustratively, can be 20 DEG C, 25 that control reaction temperature, which is 20-60 DEG C, during the liquid-liquid coprecipitation reaction
DEG C, 28 DEG C, 30 DEG C, 33 DEG C, 35 DEG C, any or any range between the two in 38 DEG C etc.), and be passed through inert atmosphere, such as N2
Atmosphere or Ar atmosphere are protected, and the pH value for controlling reaction system be 7-12 (illustratively, can be 7,8,9,9.5,10,
11, any or any range between the two in 12 etc.), the pH value of reaction system is preferably adjusted with the ammonia spirit of 3mol/L；
Preferably, reactant be pumped into speed be 10ml/min~20ml/min (illustratively, can be 10ml/min,
11ml/min、12ml/min、13ml/min、14ml/min、15ml/min、16ml/min、17ml/min、18ml/min、19ml/
Any or any range between the two in min, 20ml/min etc.), 40~60 DEG C of reaction temperature (illustratively, can be 40
DEG C, 43 DEG C, 45 DEG C, 48 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C, any or any range between the two in 60 DEG C etc.)；
Processing is filtered to above-mentioned sediment again, obtains filtered sediment；Filtered sediment is carried out again
Cleaning treatment (cleaning agent illustratively, used can for deionized water, ultrapure water, dehydrated alcohol or acetone any one or
Any a variety of mixture), then in vacuum drying oven in 80-110 DEG C of temperature (illustratively, can for 80 DEG C, 85 DEG C, 90 DEG C,
Any or any range between the two in 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C etc.), vacuum degree≤10.0Pa is (illustratively,
Can be any in 10Pa, 8Pa, 6Pa, 5Pa, 4Pa, 2Pa, 1Pa, 0.5Pa etc. or any range between the two) under carry out it is true
It (can be illustratively, model between the two any or any in 2h, 3h, 3.5h, 4h, 5h, 6h etc. that sky, which is dried 2h~6h,
Enclose), obtain presoma.
The presoma is nanometer sheet, nanometer sheet with a thickness of 5-50nm, nanometer sheet diameter is 50-500nm.
This step prepares nano-sheet presoma using template assembling-coprecipitation, and with a thickness of 5-50nm, diameter is
50-500nm；It is assembled using template, assembles the template of slabbing first in the solution, then the reactor under the limitation of template
In metal salt chemically reacted with precipitating reagent, to obtain the carbonate substance or hydroxide species nanometer sheet of the metal
Shape presoma precipitating；It is self-assembled into sheet soft template using template, on the basis of this template obtained by chemical coprecipitation reaction
Flaky nanometer structure is also formed to presoma precipitating, which has many advantages, such as that large specific surface area, reactivity are high.
Compared with traditional chemical coprecipitation, the nanometer sheet presoma ternary obtained or rich lithium manganese base solid solution positive electrode electricity
Chemical property is excellent；
Presoma nanometer sheet prepared by this step can reduce height convenient for the infiltration and reaction of lithium salts in later period sintering process
Warm sintering time, be sintered 8-10 hours can be obtained finished product in a preferred embodiment, to reduce energy consumption；
Nano-sheet presoma prepared by this step can be sintered the ternary for preparing Nano grade or lithium-rich manganese-based solid
Solution positive electrode, and prepared positive electrode has preferable chemical property, and high rate performance significantly improves；
The nano-sheet ternary or rich lithium manganese base solid solution positive electrode of this step preparation have bigger serface, high stable
Property, high capacity, high conductivity, can be used for the preparation of high performance lithium ion battery electrode anode material.
Step 4: heat treatment:, (illustratively, can be in 600 DEG C~1000 DEG C of temperature after presoma is mixed with lithium salts
For any in 600 DEG C, 700 DEG C, 800 DEG C, 850 DEG C, 950 DEG C, 1000 DEG C etc. or any range between the two) it is heat-treated
Not less than 6h, preferably 8-10h (illustratively, can for it is any in 8h, 8.5h, 9h, 9.5h, 10h etc. or it is any between the two
Range), obtain nano-sheet ternary or rich lithium manganese base solid solution positive electrode.
Above-mentioned lithium salts is Li2CO3When, the mole ratio of above-mentioned presoma and lithium salts is 1:(0.5-0.7), preferably 1:
(0.51-0.65)；Above-mentioned lithium salts is LiOH, LiNO3、LiC2H3O2One of when, the mole ratio of above-mentioned presoma and lithium salts
For 1:(1-1.5), preferably 1:(1-1.2)；
The heat treatment time of this step significantly shortens, and improves production efficiency.
Preparation method simple process provided by this method, environmental-friendly, energy-efficient, product quality is uniform, repeatability
Good, gained nanometer sheet is easily dispersed, and is produced on a large scale.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the invention.Externally it should be understood that after reading the contents of the present invention, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1:
Rich lithium manganese base solid solution material precursor manufactured in the present embodiment is to prepare nano-sheet using molecular template agent method
The preparation method of rich lithium manganese base solid solution positive electrode material precursor, molecular formula Mn0.54Ni0.13Co0.13(OH)2；The present embodiment
The method for preparing rich lithium manganese base solid solution positive electrode, comprising the following steps:
(1) prepared by metal salt solution: weighing the nitre of the manganese nitrate of 0.54mol, the nickel nitrate of 0.13mol, 0.13mol respectively
Sour cobalt, is dissolved in ultrapure water, is configured to 4 liters of solution, so that it is molten to obtain the metal salt that metal cation concentration is 0.2mol/L
Liquid.
(2) precipitating reagent and the preparation of template mixed solution: the sodium hydroxide of 1.64mol is weighed, is dissolved in ultrapure water, is prepared
At 4 liters of aqueous solution, the precipitant solution that concentration is 0.41mol/L is obtained；Polyvinylpyrrolidone (4000), second two are weighed again
Each 0.4mol of alcohol is dissolved in the precipitant solution, and it is molten for precipitating reagent and the template mixing of 0.2mol/L to be configured to template agent concentration
Liquid.
(3) template solution (polyvinylpyrrolidone of the 0.2mol/L of 40ml precursor preparation: is added in the reactor
(4000) and the concentration of ethylene glycol is 0.1mol/L), then mixed above-mentioned metal salt solution, precipitating reagent and template with peristaltic pump
It closes solution to be pumped into reactor simultaneously by the volume ratio of 1:1, carries out liquid-liquid coprecipitation reaction, it is 20ml/ that reactant, which is pumped into speed,
Min is passed through N2Inert gas shielding, 20~60 DEG C of reaction temperature, the pH value of reaction system controls between 9-11, with ammonium hydroxide tune
The pH value for saving reaction solution, obtains sediment；
Processing is filtered to sediment again, obtains filtered sediment；Again to filtered sediment cleaning agent
(can be deionized water, ultrapure water, dehydrated alcohol or acetone any one or any a variety of mixture) starts the cleaning processing,
110 DEG C are warming up in vacuum drying oven again, vacuum drying treatment 2h is carried out under vacuum degree≤10.0Pa, obtains presoma, point
Minor is Mn0.54Ni0.13Co0.13(OH)2；The presoma is nanometer sheet, and the thickness of nanometer sheet is about 10nm, and nanometer sheet diameter is about
For 300nm.
(4) it is heat-treated: after the presoma of 0.1mol is mixed with the lithium carbonate of 0.061mol, being heat-treated in 800 DEG C
10 hours, obtain rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2。
Fig. 1 is the presoma Mn of embodiment preparation0.54Ni0.13Co0.13(OH)2Scanning electron microscope (SEM) figure
Piece；It can be seen that gained presoma Mn from above-mentioned picture0.54Ni0.13Co0.13(OH)2Most of flaky nanometer structures (A in Fig. 1,
B), together, it can be seen that nanometer sheet thickness is in 10nm or so in Figure 1B, the diameter of piece is in 300nm for part flaky material " viscous "
Left and right.
Fig. 2 is rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2SEM picture.With its presoma
Pattern is compared, rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2Thickness increase it is obvious, but still
There can be the particle of part that there is layer structure feature, especially performance becomes apparent in fig. 2b；Similar hexagonal slab thickness
About 200 nanometers, width is 1 microns.
Fig. 3 is rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2X-ray diffractogram (XRD)；It should
Figure is typical α-NaFeO2Type layer structure XRD spectrum illustrates that the material obtained is single pure phase without other miscellaneous peaks.
Fig. 4 is prepared rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2First charge-discharge it is bent
Line, discharge capacity is 278mAh/g for the first time.
Fig. 5 is prepared rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2Charge and discharge cycles it is bent
Line, the special capacity fade very little of material after 30 charge and discharge illustrate that material has preferable cyclical stability.
Embodiment 2:
Ternary solid solution material precursor manufactured in the present embodiment is to prepare nano-sheet ternary using molecular template agent method
The preparation method of solid solution cathode material presoma, molecular formula Ni0.334Mn0.333Co0.333(OH)2, the present embodiment preparation richness
The method of lithium manganese based solid solution positive electrode, comprising the following steps:
(1) prepared by metal salt solution: weighing the manganese nitrate of 0.333mol, the nickel nitrate of 0.334mol, 0.333mol respectively
Cobalt nitrate be dissolved in ultrapure water, be configured to 1 liter of solution, thus obtain metal cation concentration be 1mol/L metal salt it is molten
Liquid.
(2) precipitating reagent and the preparation of template mixed solution: the sodium hydroxide for weighing 2.1mol is dissolved in ultrapure water, is configured to
1 liter of precipitant solution, obtaining concentration is 2.1mol/L precipitant solution；Take myristyl sodium phosphate, polyvinylpyrrolidone
(4000), each 0.333mol of hydroxyethyl piperazine second thiosulfonic acid is dissolved in precipitant solution, and being configured to template agent concentration is 1mol/
The precipitating reagent and template mixed solution of L.
(3) precursor preparation: in the reactor be added 20ml 1mol/L template solution (myristyl sodium phosphate,
Polyvinylpyrrolidone (4000), hydroxyethyl piperazine second thiosulfonic acid concentration be 0.333mol/L), above-mentioned metal salt is molten
Liquid, precipitating reagent and template mixed solution are pumped into reactor according to the ratio mixed solution of volume ratio 1:1, and it is total to carry out liquid-liquid
Precipitation reaction is passed through N2Inert gas shielding, wherein reactant be pumped into speed be 20ml/min, 40 DEG C of reaction temperature, reactant
The pH value of system controls between 10-11.5, and the pH value of reaction solution is adjusted with ammonium hydroxide, obtains sediment；
Processing is filtered to sediment again, obtains filtered sediment；Again to filtered sediment cleaning agent
(can be illustratively, deionized water, ultrapure water, dehydrated alcohol or acetone any one or any a variety of mixture) carries out
Cleaning treatment, then 80 DEG C are warming up in vacuum drying oven, vacuum drying treatment 6h is carried out at vacuum degree≤10.0Pa, before obtaining
Drive body C Mn0.334Ni0.333Co0.333(OH)2；The presoma is nanometer sheet, and the thickness of nanometer sheet is about 10nm, nanometer sheet diameter
About 300nm.
(4) it is heat-treated: after 0.1mol presoma is mixed with the lithium carbonate of 0.051mol, being heat-treated 8 hours at 800 DEG C,
Obtain ternary solid solution positive electrode LiNi0.334Mn0.333Co0.333O2。
Fig. 6 is the presoma Ni of embodiment preparation0.334Mn0.333Co0.333(OH)2SEM picture.It can from above-mentioned picture
To find out, gained presoma Ni0.334Mn0.333Co0.333(OH)2For the nanometer sheet (Fig. 6 A, B) of accumulation, Fig. 6 B is abundant ultrasound point
SEM photograph after dissipating, it can be seen that nanometer sheet thickness is in 10nm or so in figure, the diameter of piece is in 300 rans.
The discharge capacity for the first time of the ternary solid solution positive electrode of the present embodiment is 280mAh/g, material after 30 charge and discharge
Special capacity fade very little, illustrate material have preferable cyclical stability.
Embodiment 3:
Rich lithium manganese base solid solution material precursor manufactured in the present embodiment is to prepare nano-sheet using molecular template agent method
The preparation method of rich lithium manganese base solid solution positive electrode material precursor, molecular formula Mn0.4Ni0.2Co0.2CO3；The present embodiment preparation
The method of rich lithium manganese base solid solution positive electrode, comprising the following steps:
(1) prepared by metal salt solution: weighing the sulfuric acid of the manganese sulfate of 0.8mol, the nickel sulfate of 0.4mol, 0.4mol respectively
Cobalt is dissolved in ultrapure water, is configured to 0.8 liter of solution, to obtain 2mol/L metal salt solution.
(2) precipitating reagent and the preparation of template mixed solution: the sodium carbonate of 1.68mol is weighed, is dissolved in ultrapure water, is configured to
0.8 liter of aqueous solution, obtaining concentration is 2.1mol/L precipitant solution；Cetyl trimethylammonium bromide, ethoxy are weighed again
Each 0.8mol of piperazine second thiosulfonic acid is dissolved in the precipitant solution, is configured to precipitating reagent and mould that template agent concentration is 2mol/L
Plate agent mixed solution.
(3) template solution (the cetyl trimethyl bromine of the 2mol/L of 20ml precursor preparation: is added in the reactor
Change ammonium, the concentration of hydroxyethyl piperazine second thiosulfonic acid is 1mol/L), above-mentioned metal salt solution, precipitating reagent and template are mixed
Solution is pumped into reactor by the volume ratio of 1:1, carries out liquid-liquid coprecipitation reaction, and it is 10ml/ that wherein reactant, which is pumped into speed,
Min, is passed through N by 50 DEG C of reaction temperature2Inert gas shielding is controlled between 10-11 with the pH value that ammonium hydroxide adjusts reaction system,
Obtain sediment；
Processing is filtered to sediment again, obtains filtered sediment；Again to filtered sediment cleaning agent
(can be illustratively, deionized water, ultrapure water, dehydrated alcohol or acetone any one or any a variety of mixture) carries out
Cleaning treatment, then in vacuum drying oven, 100 DEG C are warming up to, vacuum drying treatment 6h is carried out at vacuum degree≤10.0Pa, is obtained
Presoma, molecular formula Mn0.4Ni0.2Co0.2CO3；The presoma is nanometer sheet, and the thickness of nanometer sheet is about 20nm, nanometer sheet
Diameter is about 300nm.
(4) it is heat-treated: after 0.1mol presoma is mixed with the lithium carbonate of 0.063mol, carrying out heat treatment 10 in 800 DEG C
Hour, obtain rich lithium manganese base solid solution positive electrode Li1.2Mn0.4Ni0.2Co0.2O2。
The discharge capacity for the first time of the rich lithium manganese base solid solution positive electrode of the present embodiment is 275mAh/g, after 30 charge and discharge
The special capacity fade very little of material illustrates that material has preferable cyclical stability.
Embodiment 4:
Rich lithium manganese base solid solution material precursor manufactured in the present embodiment is to prepare nano-sheet using molecular template agent method
The preparation method of rich lithium manganese base solid solution positive electrode material precursor, molecular formula Mn0.725Ni0.225Co0.05CO3；The present embodiment
The method for preparing rich lithium manganese base solid solution positive electrode, comprising the following steps:
(1) prepared by metal salt solution: weighing the manganese chloride of 0.725mol, the nickel sulfate of 0.225mol, 0.05mol respectively
Cobalt nitrate is dissolved in ultrapure water, is configured to 1 liter of solution, to obtain the metal salt solution of 1mol/L.
(2) precipitating reagent and the preparation of template mixed solution: weighing the sodium carbonate of 1.05mol, soluble in water, is configured to 1 liter
Aqueous solution, obtain concentration be 1.05mol/L precipitant solution；Take polyvinylpyrrolidone (4000), each 0.5mol of ethylene glycol
It is dissolved in the precipitant solution, is configured to the precipitating reagent and template mixed solution that template agent concentration is 1mol/L.
(3) template solution (template, the polyethylene pyrrole of the 1mol/L of 40ml precursor preparation: are added in the reactor
The concentration of pyrrolidone (4000) is 0.5mol/L), above-mentioned metal salt solution, precipitating reagent and template mixed solution are pressed into 1:1
Volume ratio be pumped into reactor, carry out liquid-liquid coprecipitation reaction, be passed through Ar inert gas shielding, wherein reactant is pumped into speed
Degree is 15ml/min, 55 DEG C of reaction temperature, is controlled between 8-10 with the pH value that ammonium hydroxide adjusts reaction system, obtains sediment；
Processing is filtered to sediment again, obtains filtered sediment；Again to filtered sediment cleaning agent
(can be illustratively, deionized water, ultrapure water, dehydrated alcohol or acetone any one or any a variety of mixture) carries out
Cleaning treatment, then in vacuum drying oven, 110 DEG C are warming up to, vacuum drying treatment 2h is carried out at vacuum degree≤10.0Pa, is obtained
Presoma；The presoma is nanometer sheet, and the thickness of nanometer sheet is about 9nm, and nanometer sheet diameter is about 200nm.
(4) it is heat-treated: after 0.1mol presoma is mixed with the lithium carbonate of 0.063mol, being heat-treated 8 hours at 1000 DEG C,
Obtain rich lithium manganese base solid solution positive electrode Li1.2Mn58Ni0.18Co0.04O2。
The discharge capacity for the first time of the rich lithium manganese base solid solution positive electrode of the present embodiment is 281mAh/g, after 30 charge and discharge
The special capacity fade very little of material illustrates that material has preferable cyclical stability.
Embodiment 5:
Rich lithium manganese base solid solution material precursor manufactured in the present embodiment is to prepare nano-sheet using molecular template agent method
The preparation method of rich lithium manganese base solid solution positive electrode material precursor, molecular formula Mn0.675Ni0.1625Co0.1625CO3；This implementation
The method of example preparation rich lithium manganese base solid solution positive electrode, comprising the following steps:
(1) metal salt solution prepare: weigh respectively the manganese nitrate of 0.135mol, the nickel nitrate of 0.0325mol,
The cobalt nitrate of 0.0325mol is dissolved in ultrapure water, is configured to 2 liters of solution, to obtain the metal salt solution of 0.1mol/L.
(2) precipitating reagent and the preparation of template mixed solution: the sodium carbonate of 0.21mol is weighed, is dissolved in ultrapure water, is configured to
2 liters of aqueous solution, obtaining concentration is 0.105mol/L precipitant solution；Take polyvinylpyrrolidone (4000), ethylene glycol each
0.05mol is dissolved in the precipitant solution, and it is molten for precipitating reagent and the template mixing of 0.05mol/L to be configured to template agent concentration
Liquid.
(3) template solution (polyvinylpyrrolidine of the 0.05mol/L of 30ml precursor preparation: is added in the reactor
The concentration of ketone (4000) and ethylene glycol is 0.025mol/L), by above-mentioned metal salt solution, precipitating reagent and template mixed solution
It is pumped into reactor, carries out liquid-liquid coprecipitation reaction, it is 50ml/min that wherein reactant, which is pumped into speed, 50 DEG C of reaction temperature, is led to
Enter N2Inert gas shielding is controlled between 9-11 with the pH value that ammonium hydroxide adjusts reaction system, obtains sediment；
Processing is filtered to sediment again, obtains filtered sediment；Again to filtered sediment cleaning agent
(can be illustratively, deionized water, ultrapure water, dehydrated alcohol or acetone any one or any a variety of mixture) carries out
Cleaning treatment, then in vacuum drying oven, 100 DEG C are warming up to, vacuum drying treatment 3h is carried out at vacuum degree≤10.0Pa, is obtained
Presoma；The presoma is nanometer sheet, and the thickness of nanometer sheet is about 13nm, and nanometer sheet diameter is about 300nm.
(4) it is heat-treated: after 0.1mol presoma is mixed with the lithium carbonate of 0.052mol, carrying out heat treatment 8- in 950 DEG C
20 hours, obtain rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2。
The discharge capacity for the first time of the rich lithium manganese base solid solution positive electrode of the present embodiment is 285mAh/g, after 30 charge and discharge
The special capacity fade very little of material illustrates that material has preferable cyclical stability.
Embodiment 6:
Rich lithium manganese base solid solution material precursor manufactured in the present embodiment is to prepare nano-sheet using molecular template agent method
The preparation method of rich lithium manganese base solid solution positive electrode material precursor, molecular formula Mn0.675 0.1625Co0.1625(OH)2；This implementation
The method of example preparation rich lithium manganese base solid solution positive electrode, comprising the following steps:
(1) prepared by metal salt solution: weighing the manganese chloride of 1.35mol, the nickel chloride of 0.325mol, 0.325mol respectively
Cobalt chloride is dissolved in ultrapure water, is configured to 1 liter of solution, to obtain the metal salt solution of 2mol/L.
(2) precipitating reagent and the preparation of template mixed solution: weighing the sodium hydroxide of 4.2mol, soluble in water, is configured to 1 liter
Aqueous solution, obtain concentration be 4.2mol/L precipitant solution；Take cetyl trimethylammonium bromide, hydroxyethyl piperazine second sulphur
Each 1mol of acid is dissolved in the precipitant solution, and it is molten for precipitating reagent and the template mixing of 2mol/L to be configured to template agent concentration
Liquid.
(3) template solution (the cetyl trimethyl bromine of the 2mol/L of 40ml precursor preparation: is added in the reactor
Change ammonium, the concentration of hydroxyethyl piperazine second thiosulfonic acid is 1mol/L), above-mentioned metal salt solution, precipitating reagent and template are mixed
Solution is pumped into reactor by the volume ratio of 1:1, carries out liquid-liquid coprecipitation reaction, and it is 10ml/ that wherein reactant, which is pumped into speed,
Min, is passed through N by 60 DEG C of reaction temperature2Inert gas shielding, with ammonium hydroxide adjust reaction system pH value control 10-11.5 it
Between, obtain sediment；Processing is filtered to sediment again, obtains filtered sediment；Filtered sediment is used again
Cleaning agent (can be illustratively, deionized water, ultrapure water, dehydrated alcohol or acetone any one or any a variety of mixing
Object) it starts the cleaning processing；Again in vacuum drying oven, 100 DEG C are warming up to, is carried out at vacuum drying at vacuum degree≤10.0Pa
Reason, 3h obtain presoma；The presoma is nanometer sheet, and the thickness of nanometer sheet is about 30nm, and nanometer sheet diameter is about 200nm.
(4) it is heat-treated: after 0.1mol presoma is mixed with the lithium carbonate of 0.065mol, being heat-treated 12 hours at 850 DEG C,
Obtain rich lithium manganese base solid solution positive electrode Li1.2Mn0.54Ni0.13Co0.13O2。
The discharge capacity for the first time of the rich lithium manganese base solid solution positive electrode of the present embodiment is 277mAh/g, after 30 charge and discharge
The special capacity fade very little of material illustrates that material has preferable cyclical stability.
Claims (6)
1. the preparation method of a kind of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor, it is characterised in that: should
Method includes the following steps:
Metal salt solution preparation step: manganese salt, cobalt salt and nickel salt are mixed with water, and dissolution obtains metal salt solution；
Precipitating reagent and template mixed solution preparation step: the dissolution soluble in water of precipitating reagent, template is taken, precipitating reagent and mould are obtained
Plate agent mixed solution；
Precursor preparation step: first compound concentration is identical as the concentration of template in the precipitating reagent and template mixed solution
Template solution, be placed in reactor, then the metal salt solution, precipitating reagent and template mixed solution are pumped into reactor
Interior progress liquid-liquid coprecipitation reaction, obtains sediment；Processing is filtered to the sediment again, obtains filtered precipitating
Object；The filtered sediment is started the cleaning processing again, vacuum drying treatment, obtains the presoma；
In the precipitating reagent and template mixed solution preparation step, the precipitating reagent is lithium hydroxide, ammonium hydrogen carbonate or carbonic acid
One of ammonium is a variety of；The concentration of the precipitating reagent is 0.0105~2.1mol/L；
In the precipitating reagent and template mixed solution preparation step, the template is polyvinylpyrrolidone, dodecyl
Sulfonate, cetyl trimethylammonium bromide, myristyl phosphate, polyester polyol, in hydroxyethyl piperazine second thiosulfonic acid
It is one or more；The concentration of the template is 0.001~0.5 mol/L；
In the liquid-liquid coprecipitation reaction of the precursor preparation step, temperature is 20-60 DEG C；The pH value of reaction system is
7-12；The liquid-liquid coprecipitation reaction carries out under inert atmosphere protection；
The presoma is nanometer sheet；The nanometer sheet with a thickness of 5~50 nm, the nanometer sheet diameter is 50~500 nm.
2. the preparation method of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor according to claim 1,
It is characterized by:
In the metal salt solution preparation step and the precipitating reagent and template mixed solution preparation step, the water be go from
Sub- water.
3. the preparation side of nano-sheet ternary according to claim 1 or claim 2 or rich lithium manganese base solid solution positive electrode material precursor
Method, it is characterised in that:
In metal salt solution preparation step,
The manganese salt are as follows: one of manganese nitrate, manganese acetate, manganese chloride and manganese sulfate are a variety of；
The nickel salt are as follows: one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate are a variety of；
The cobalt salt are as follows: one of cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate are a variety of.
4. the preparation method of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor according to claim 3,
It is characterized by:
In the metal salt solution of the metal salt solution preparation step, metal cation concentration be 0.01mol/L~
2.0mol/L。
5. the preparation side of nano-sheet ternary according to claim 1 or claim 2 or rich lithium manganese base solid solution positive electrode material precursor
Method, it is characterised in that:
The inert atmosphere is N2Atmosphere or Ar atmosphere.
6. the preparation method of nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor according to claim 1,
It is characterized by: in the vacuum drying treatment of the precursor preparation step, temperature is 80~110 DEG C, vacuum degree be less than or
Equal to 10.0Pa, the time is 2~6 hours.
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| CN108054371B (en) * | 2017-12-21 | 2020-08-07 | 哈尔滨工业大学 | Lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life and preparation method thereof |
| CN108232187B (en) * | 2018-01-03 | 2020-03-10 | 武汉科技大学 | High-dispersion hexagonal nanosheet structure nickel-cobalt-manganese ternary cathode material and preparation method thereof |
| CN108598463B (en) * | 2018-02-28 | 2020-11-17 | 中国电力科学研究院有限公司 | Preparation method of nano flaky lithium-rich manganese-based positive electrode material |
| CN108470906A (en) * | 2018-03-02 | 2018-08-31 | 河南师范大学 | The method for preparing high-performance sodium-ion battery positive material using double template |
| CN109742337B (en) * | 2018-12-07 | 2022-03-29 | 北京理工大学 | Ternary cathode material precursor and method for regulating crystal face growth of ternary cathode material precursor |
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| CN110429267A (en) * | 2019-08-19 | 2019-11-08 | 河南师范大学 | The method for preparing nanoscale flake sodium-ion battery positive material using multi-template agent |
| CN111180722B (en) * | 2020-01-08 | 2022-09-27 | 太原理工大学 | Preparation method of lithium ion battery anode material nickel cobalt lithium aluminate |
| CN111293305B (en) * | 2020-02-20 | 2023-05-30 | 中南大学 | Hexagonal flaky nickel cobalt lithium manganate precursor and preparation method thereof |
| CN111640923B (en) * | 2020-06-01 | 2021-12-10 | 广州大学 | Lithium nickel manganese oxide positive electrode material and preparation method thereof |
| CN113603144A (en) * | 2021-07-30 | 2021-11-05 | 高点(深圳)科技有限公司 | Preparation method of modified manganese hydroxide, product and application thereof |
| CN115959713A (en) * | 2021-10-11 | 2023-04-14 | 中国科学院过程工程研究所 | Lithium ion battery anode material and preparation method and application thereof |
| CN114988479A (en) * | 2022-05-20 | 2022-09-02 | 上海锦源晟新能源材料有限公司 | Manganese-containing material and preparation method thereof, and lithium manganate and preparation method and application thereof |
| CN116443945B (en) * | 2023-02-21 | 2024-07-09 | 广东邦普循环科技有限公司 | Lithium-rich manganese-based mesoporous cathode material and preparation method and application thereof |
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