CN106025262A - Method for preparing nanometer spinel lithium nickel manganese oxide - Google Patents

Method for preparing nanometer spinel lithium nickel manganese oxide Download PDF

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CN106025262A
CN106025262A CN201610573614.8A CN201610573614A CN106025262A CN 106025262 A CN106025262 A CN 106025262A CN 201610573614 A CN201610573614 A CN 201610573614A CN 106025262 A CN106025262 A CN 106025262A
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spinel type
nanometer
preparation
nanometer spinel
ion doped
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CN106025262B (en
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周继承
隗小山
张祖喜
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Xiangtan University
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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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 provides a method for preparing nanometer spinel lithium nickel manganese oxide. The method includes steps of uniformly mixing manganese salt, lithium salt and nickel salt with one another to obtain mother liquor with the total cation concentration of 0.1-1.0 mol/L, carrying out liquid-liquid co-precipitation reaction on the mother liquor to prepare nanometer precursors and adding the nanometer precursors into ammonium carbonate solution under the condition that the rotational speeds of rotors of a high-gravity reactor are 400-2200 rpm; continuously recycling mixed liquor under the effects of high-gravity fields until reaction is completely carried out to obtain suspension; filtering the suspension and then drying to obtain precursors; calcining the precursors in a microwave muffle furnace to obtain the nanometer spinel lithium nickel manganese oxide. The method has the advantages that the spinel lithium nickel manganese oxide which is high in crystallinity, complete in crystal form and good in dispersibility, contains uniform particles and has controllable particle sizes can be prepared by the aid of the method, and the average particle sizes of the spinel lithium nickel manganese oxide can reach 50-100 nm; the method includes simple processes, is low in cost and good in batch production stability and is environmentally friendly.

Description

A kind of preparation method of nanometer spinel type nickel ion doped
Technical field
The present invention relates to lithium ion battery material preparing technical field, be specifically related to a kind of nanometer spinel type nickel ion doped LiNi0.5Mn1.5O4Preparation method.
Background technology
In numerous anode material for lithium-ion batteries, the nickel ion doped material of spinel-type is because himself having the high electricity of 4.7V The advantages such as pressure, good cycle performance, it is possible to fully meet the needs of green new kinetic energy, such as: the nickel ion doped of spinel-type Material is compared to cobalt acid lithium material, and its production cost is low, environmental pollution is little;The nickel ion doped material of spinel-type is compared to manganese Acid lithium material, the stability under high temperature circulation is preferable;The nickel ion doped material of spinel-type compared to LiFePO 4 material, Its synthesis technique is simple, and stability in batch production is good, the cell assembled when especially matching with lithium titanate anode, defeated Going out voltage and may be up to 3.2V, overall performance advantage is clearly.Nickel ion doped belongs to inorganic metal composite oxides, therefore, The synthetic method of general inorganic material may be used to synthesize nickel ion doped.
Spinel-type nickel ion doped is as lithium ion anode material, and its voltage platform is high, thermal cycling stability is good, discharge and recharge Speed is fast.Ni in charging process, in nickel ion doped material4+、Mn4+3d electron orbit and O2-In 2p electronics Track hydridization effectively, reaches mutual steady statue, and then overcomes the analysis oxygen problem of material.Further, since nickel mangaic acid Lithium material contains the formation of positive Manganic ion, substantially eliminates capacity fade problem, therefore, fundamentally improves material and exist The stability of cycle charge-discharge.Prior art prepares the method for spinel-type nickel ion doped to be had:
Patent of invention CN102569776A discloses a kind of employing hydro-thermal one solid phase two-step method and prepares spherical high-voltage positive pole material The method of material spinel-type nickel ion doped, specifically: first by the carbon of nickel source, manganese source and doping element compound solution Yu sodium/ammonium Acid salt solution mix homogeneously, then it is added thereto to surfactant, prepare class spherical nickel-manganese carbonate under hydrothermal conditions Co-precipitation;The dried sintering of washing obtains spherical nickel-manganese oxide;Oxide is mixed through liquid phase ball milling with lithium source, is dried, Finally sintering obtains positive electrode active materials.The method complex process, can only prepare spherical nickel ion doped.
Patent of invention CN103280570A discloses the preparation method of a kind of micron-order single-crystal nickel lithium manganate anode material, tool Body is: prepares nickel-manganese composite hydroxide, nickel manganese oxide complex hydroxide in solution, obtains complex chemical compound seed crystal;In By nickel salt, manganese salt and alkali compounds hybrid reaction in solution, and aoxidize simultaneously, make complex chemical compound seed crystal grow up to Particle diameter is 0.1~30 micron;The crystal grain obtained directly is mixed in the solution with lithiumation thing, or by crystal grain acid Mix with lithiumation thing after process, in oxidative environment, then carry out oxidation reaction, be dried after filtration, roasting nickel ion doped The presoma of compound.The method preparation technology is simple, can obtain mono-crystalline structures, the nickel ion doped material of high-energy-density, But its particle size is micron order, it is difficult to reach Nano grade.
Application for a patent for invention CN105047900A provides the preparation method of a kind of nano-sheet nickel mangaic acid file material, specifically Being: water-soluble salt of nickel and manganese is configured to solution to add precipitant with chelating agent after reacting, reaction obtains nickel manganese and closes Thing presoma, roasting obtains Ni, Mn oxide;Ni, Mn oxide and lithium compound mixing, spinel-type nickel manganese is prepared in high-temperature roasting Acid lithium compound;By being coated with one layer of uniform titanium and/or the metal-oxide of zirconium at particle surface, prepared by the modification of surface Spinel-type nickel ion doped compound.Though the spinel nickel mangaic acid file material prepared from method has nano-grade size, but it is micro- Sight pattern is lamellar, and degree of crystallinity is the highest, it is difficult to directly applied to the preparation of spinel-type nickel ion doped.
In sum, urgent need exploitation is a kind of can prepare the nano-grade spinel type nickel ion doped demand with satisfied reality.
Summary of the invention
Present invention aim at providing the preparation method of a kind of nanometer spinel type nickel ion doped, comprise the following steps:
The first step, prepare presoma, specifically:
Lithium salts, nickel salt and manganese salt distilled water are dissolved and is configured to mixed solution;Mixed solution is passed through hypergravity anti- Answer in device;Add precipitant, continue reaction, reacted and i.e. obtained reactant liquor;Obtain with the pH value of ammonia regulation reactant liquor To reaction slurry;Reaction slurry is carried out heating in water bath anhydrate and be dried, obtain presoma;
Second step, prepare nanometer spinel type LiNi0.5Mn1.5O4, specifically:
First step gained presoma is calcined under microwave heating, obtains nanometer spinel type LiNi0.5Mn1.5O4 Powder.
In above technical scheme preferably, described supergravity reactor is rotating bed with helix channel or RPB, institute The rotor speed stating supergravity reactor is 300-1500r/min, preferably 700-1200r/min.
In above technical scheme preferably, lithium ion pressed by described lithium salts, nickel salt, manganese salt: nickel ion: manganese ion mole Dispensing is carried out than the proportioning for 1-1.1:0.5:1.5;The cation total concentration of described mixed solution is 0.1-0.5mol/L.
In above technical scheme preferably, described mixed solution is passed through hypergravity reaction continuously with the speed of 200-500L/h In device, circulate 10-30min;Drip precipitant with 100ml per minute, continue reaction 20-50min after being added dropwise to complete and obtain To reactant liquor;The pH value of described reaction slurry is 7.0-9.0.
In above technical scheme preferably, described precipitant is sal volatile, the concentration of ammonium ion in described sal volatile Total cation concentration for mixed solution.
In above technical scheme preferably, described heating in water bath anhydrates specifically: by being 60 DEG C-120 DEG C in temperature Under the conditions of water-bath transpiring moisture, preferable temperature is 80 DEG C-120 DEG C;Described be dried specifically: in temperature be 6-24h it is dried under conditions of 100 DEG C-180 DEG C.
In above technical scheme preferably, described second step is calcined specifically: with the speed of 5 DEG C/min-30 DEG C/min It is warming up to 780 DEG C-900 DEG C, under the conditions of 780 DEG C-900 DEG C, calcines 1.5-2.5h.
In above technical scheme preferably, described second step is calcined specifically: with the ramp of 10 DEG C/min extremely 850 DEG C, under the conditions of 850 DEG C, calcine 2h.
In above technical scheme preferably, described nickel salt is nickel nitrate, and described manganese salt is manganese nitrate, and described lithium salts is lithium nitrate.
Apply nanometer spinel type LiNi of the present invention0.5Mn1.5O4Preparation method, have the advantages that
(1) a kind of method that the present invention provides novel preparation nano nickel lithium manganate, can prepare mean diameter is 50-100nm, degree of crystallinity are high, crystal formation is complete, granule is uniform, size tunable and the nanometer spinel type nickel mangaic acid of good dispersion Lithium, overcome prior art prepare nickel ion doped particle diameter skewness, easily reunite, crystalline phase purity is low, degree of crystallinity is the most high Shortcoming.
(2) presoma of the present invention prepares (preferably with gas-liquid reaction or liquid-liquid reactions) under Elevated Gravity, overweight Power reaction microcosmic mix homogeneously, greatly strengthen mass transfer, it is ensured that the granularity of presoma is controlled and is evenly distributed.
(3) present invention prepares presoma under Elevated Gravity, then is calcined presoma by microwave heating, Calcination process homogeneous temperature is controlled and without thermograde, it is ensured that product particle size is uniform, degree of crystallinity is high.
(4) the process step of the invention is simplified, and equipment is readily obtained, with short production cycle, is suitable for industrialized production.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.Under Face will be with reference to figure, and the present invention is further detailed explanation.
Accompanying drawing explanation
The accompanying drawing of the part constituting the application is used for providing a further understanding of the present invention, the illustrative examples of the present invention And explanation is used for explaining the present invention, it is not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is nanometer spinel type LiNi prepared by the preferred embodiment of the present invention 10.5Mn1.5O4XRD spectra;
Fig. 2 is nanometer spinel type LiNi prepared by the preferred embodiment of the present invention 10.5Mn1.5O4SEM spectrogram;
Fig. 3 is nanometer spinel type LiNi prepared by the preferred embodiment of the present invention 10.5Mn1.5O4TEM spectrogram;
Fig. 4 is the XRD spectra of the sample of embodiment 1-embodiment 3 (under reaction mass different conditions of mixture ratios);
Fig. 5 is the XRD spectra of the sample of embodiment 1, embodiment 4 and embodiment 5 (reactant liquors of different pH value);
Fig. 6 is the XRD spectra of the sample of embodiment 1 (supergravity reactor) and comparative example 1 (conventional reactor);
Fig. 7 is the XRD spectra of the sample of embodiment 1 (microwave calcination) and comparative example 2 (Conventional calcination).
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are described in detail, but the present invention can according to claim limit and The multitude of different ways covered is implemented.
Embodiment 1:
A kind of nanometer spinel type nickel ion doped (LiNi0.5Mn1.5O4) preparation method, comprise the following steps:
The first step, prepare presoma, specifically:
Lithium salts, nickel salt and manganese salt distilled water are dissolved and is configured to the mixed solution that total cation concentration is 0.24mol/L; Mixed solution is passed through in supergravity reactor (specifically: first mixed solution is poured into the rotation of helical duct type hypergravity In the reservoir of rotated bed reactor, run supergravity reactor, by frequency conversion instrument regulation revolving bed rotor speed be 1000r/min, opens centrifugal pump simultaneously, makes mixed solution circulate in super-gravity device, and passes through spinner It is 400L/h that meter controls flow, circulates 10min);Add sal volatile as precipitant (ammonium in sal volatile The concentration of ion is the total cation concentration of mixed solution, and drop rate is 100ml per minute), continue reaction 30min, React and i.e. obtained reactant liquor;It is 8.0 with the pH value of ammonia regulation reactant liquor, obtains reaction slurry;Reaction slurry is entered Row heating in water bath anhydrates and is dried, and obtains presoma, and described heating in water bath anhydrates specifically: by being 90 DEG C in temperature Under conditions of water-bath transpiring moisture;Described be dried specifically: under conditions of temperature is 120 DEG C be dried 12h.
Second step, prepare nanometer spinel type LiNi0.5Mn1.5O4, specifically:
First step gained presoma is calcined under microwave heating, obtains nanometer spinel type LiNi0.5Mn1.5O4 Powder, calcining specifically: with the ramp of 10 DEG C/min to 850 DEG C, under the conditions of 850 DEG C, calcine 2h.
Described lithium salts, nickel salt, manganese salt are respectively lithium nitrate, nickel nitrate and manganese nitrate, described lithium nitrate, nickel nitrate and nitric acid Manganese is by lithium ion: nickel ion: the mol ratio of manganese ion is that the proportioning of 1:0.5:1.5 carries out dispensing.
By the present embodiment gained nanometer spinel type LiNi0.5Mn1.5O4Carry out XRD and SEM detection, the results detailed in Fig. 1, Fig. 2 and Fig. 3.From Fig. 1, Fig. 2 and Fig. 3: spinelle LiNi prepared by the present embodiment0.5Mn1.5O4Sample, has The features such as degree of crystallinity is high, crystal formation is complete, granule is uniform, size tunable, good dispersion, mean diameter is up to 50~100nm.
Embodiment 2-embodiment 3
Embodiment 2-embodiment 3 difference from Example 1 is that described lithium nitrate, nickel nitrate are different with the proportioning of manganese nitrate, Specifically: described in embodiment 2, lithium ion pressed by lithium nitrate, nickel nitrate and manganese nitrate: nickel ion: the mol ratio of manganese ion Proportioning for 1.05:0.5:1.5 carries out dispensing;Lithium ion pressed by lithium nitrate, nickel nitrate and manganese nitrate described in embodiment 3: Nickel ion: the mol ratio of manganese ion is that the proportioning of 1.1:0.5:1.5 carries out dispensing.
Embodiment 2 and embodiment 3 gained nanometer spinel type LiNi0.5Mn1.5O4XRD testing result refer to Fig. 4, As seen from Figure 4, the proportioning of lithium nitrate, nickel nitrate and manganese nitrate is important, according to embodiment 2 and embodiment 3 Spinelle LiNi prepared by proportioning0.5Mn1.5O4In all have the impurity of a small amount of Ni, Mn oxide, it is therefore preferable that lithium nitrate, nitric acid Nickel and manganese nitrate are by lithium ion: nickel ion: the mol ratio of manganese ion is that the proportioning of 1.0:0.5:1.5 carries out dispensing.
Embodiment 4-embodiment 5
Embodiment 4-embodiment 5 difference from Example 1 is that the pH value of described system is different, and concrete example 4 is to use Ammonia (NH3H2O) pH value of regulation reaction system is 7.5.In embodiment 5, use ammonia (NH3H2O) regulation is anti- The pH value answering system is 8.5.Other operating conditions are the most identical.
Embodiment 4 and embodiment 5 gained nanometer spinel type LiNi0.5Mn1.5O4XRD testing result refer to Fig. 5, As can be seen from Figure 5: when regulating pH value to 8, the sample crystallinity prepared is high, and free from admixture produces.
Comparative example 1
Comparative example 1 difference from Example 1 is:
Mixed solution is placed in the there-necked flask with stirring paddle, and stir speed (S.S.) is 1000r/min;
Add sal volatile to react 30min as precipitant, continuation, reacted and i.e. obtained reactant liquor;
It is 8.0 with the pH value of ammonia regulation reactant liquor, obtains reaction slurry;
Reaction slurry is carried out heating in water bath anhydrate and be dried, obtain presoma.
Comparative example 1 gained nanometer spinel type LiNi0.5Mn1.5O4XRD testing result refer to Fig. 6.
As shown in Figure 6: relative to conventional reactor (there-necked flask), prepared by supergravity reactor (RBHC) LiNi0.5Mn1.5O4The degree of crystallinity of powder body is higher, and crystal formation is complete.
Comparative example 2
Comparative example 2 is with the difference of embodiment 1: is calcined in conventional Muffle furnace by presoma, to obtain final product Nanometer spinel type LiNi0.5Mn1.5O4Powder, calcines specifically: warm naturally to 850 DEG C, under the conditions of 850 DEG C Calcining 10h.
Comparative example 2 gained nanometer spinel type LiNi0.5Mn1.5O4XRD testing result refer to Fig. 7, from Fig. 7 Understand: microwave calcination compares Conventional calcination, and microwave calcination not only can be effectively promoted the formation of crystalline phase, and can be greatly improved The effect of reaction, microwave calcination is more beneficial for obtaining the spinel powder material that degree of crystallinity is high, crystal formation is complete.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art For Yuan, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made, Equivalent, improvement etc., should be included within the scope of the present invention.

Claims (9)

1. the preparation method of a nanometer spinel type nickel ion doped, it is characterised in that comprise the following steps:
The first step, prepare presoma, specifically:
Lithium salts, nickel salt and manganese salt distilled water are dissolved and is configured to mixed solution;Mixed solution is passed through hypergravity anti- Answer in device;Add precipitant, continue reaction, reacted and i.e. obtained reactant liquor;Obtain with the pH value of ammonia regulation reactant liquor To reaction slurry;Reaction slurry is carried out heating in water bath anhydrate and be dried, obtain presoma;
Second step, prepare nanometer spinel type LiNi0.5Mn1.5O4, specifically:
First step gained presoma is calcined under microwave heating, obtains nanometer spinel type LiNi0.5Mn1.5O4 Powder.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 1, it is characterised in that described Supergravity reactor is rotating bed with helix channel or RPB, and the rotor speed of described supergravity reactor is 300-1500r/min, preferably 700-1200r/min.
3., according to the preparation method of the nanometer spinel type nickel ion doped described in claim 1-2 any one, its feature exists In, described lithium salts, nickel salt, manganese salt are by lithium ion: nickel ion: the mol ratio of manganese ion is 1-1.1:0.5:1.5's Proportioning carries out dispensing;The cation total concentration of described mixed solution is 0.1-0.5mol/L.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 3, it is characterised in that described Mixed solution is passed through in supergravity reactor continuously with the speed of 200-500L/h, circulates 10-30min;With per minute 10-120ml drips precipitant, continues reaction 20-50min and obtain reactant liquor after being added dropwise to complete;The pH of described reaction slurry Value is 7.0-9.0.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 4, it is characterised in that described Precipitant is sal volatile, and in described sal volatile, the concentration of ammonium ion is the total cation concentration of mixed solution.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 3, it is characterised in that described Heating in water bath anhydrates specifically: by water-bath transpiring moisture, preferable temperature under conditions of being 60 DEG C-120 DEG C in temperature It it is 80 DEG C-120 DEG C;Described be dried specifically: under conditions of temperature is 100 DEG C-180 DEG C be dried 6-24h.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 3, it is characterised in that described Second step is calcined specifically: with the ramp of 5 DEG C/min-30 DEG C/min to 780 DEG C-900 DEG C, 1.5-2.5h is calcined under the conditions of 780 DEG C-900 DEG C.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 7, it is characterised in that described Second step is calcined specifically: with the ramp of 10 DEG C/min to 850 DEG C, under the conditions of 850 DEG C, calcine 2h.
The preparation method of nanometer spinel type nickel ion doped the most according to claim 3, it is characterised in that described Nickel salt is nickel nitrate, and described manganese salt is manganese nitrate, and described lithium salts is lithium nitrate.
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CN107739057A (en) * 2017-11-03 2018-02-27 云南民族大学 A kind of preparation method of lithium manganate having spinel structure
CN109292826A (en) * 2018-07-26 2019-02-01 华南理工大学 A kind of porous lithium manganate material of high charge-discharge capacity and preparation method and application
CN109678219A (en) * 2018-12-28 2019-04-26 湘潭大学 Preparation method of nano layered lithium nickel cobalt manganese oxide
CN109935798A (en) * 2017-12-19 2019-06-25 宁波高新区锦众信息科技有限公司 A kind of preparation method of lithium ion battery nickel manganese lithium composite material
CN110282665A (en) * 2019-07-04 2019-09-27 成都尤尼瑞克科技有限公司 A kind of anode material of lithium battery presoma and preparation method thereof with mesoscopic structure
CN113120963A (en) * 2021-03-20 2021-07-16 安徽博石高科新材料股份有限公司 Preparation of lithium manganate by microwave heating and sintering

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CN106564967A (en) * 2016-10-31 2017-04-19 安泰科技股份有限公司 Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof
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CN107739057A (en) * 2017-11-03 2018-02-27 云南民族大学 A kind of preparation method of lithium manganate having spinel structure
CN109935798A (en) * 2017-12-19 2019-06-25 宁波高新区锦众信息科技有限公司 A kind of preparation method of lithium ion battery nickel manganese lithium composite material
CN109292826A (en) * 2018-07-26 2019-02-01 华南理工大学 A kind of porous lithium manganate material of high charge-discharge capacity and preparation method and application
CN109292826B (en) * 2018-07-26 2020-12-22 华南理工大学 Porous lithium manganate material with high charge-discharge capacity, and preparation method and application thereof
CN109678219A (en) * 2018-12-28 2019-04-26 湘潭大学 Preparation method of nano layered lithium nickel cobalt manganese oxide
CN109678219B (en) * 2018-12-28 2022-05-13 湘潭大学 Preparation method of nano layered lithium nickel cobalt manganese oxide
CN110282665A (en) * 2019-07-04 2019-09-27 成都尤尼瑞克科技有限公司 A kind of anode material of lithium battery presoma and preparation method thereof with mesoscopic structure
CN113120963A (en) * 2021-03-20 2021-07-16 安徽博石高科新材料股份有限公司 Preparation of lithium manganate by microwave heating and sintering

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