CN108539159A - The preparation method of multielement codope LiMn2O4 composite material - Google Patents

The preparation method of multielement codope LiMn2O4 composite material Download PDF

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CN108539159A
CN108539159A CN201810296171.1A CN201810296171A CN108539159A CN 108539159 A CN108539159 A CN 108539159A CN 201810296171 A CN201810296171 A CN 201810296171A CN 108539159 A CN108539159 A CN 108539159A
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preparation
limn2o4
composite material
temperature
codope
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卑凤利
朱律忠
陈均青
余毛省
陈俊辉
储海蓉
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection 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
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of preparation methods of multielement codope LiMn2O4 composite material.The method uses sol-gal process, first by four acetate hydrate manganese, the mixed solution of ANN aluminium nitrate nonahydrate, four acetate hydrate magnesium, four acetate hydrate cobalts, it is slowly dropped under stirring in the mixed solution of a hydronium(ion) lithia and citric acid, ammonium hydroxide is added and adjusts pH value of solution, after heating stirring is generated to colloidal sol, it is dried to obtain xerogel, will be ground into powder after xerogel pre-burning, finally calcining obtains the composite material of three element codope LiMn2O4 of aluminium cobalt magnesium.Present invention process is simple, and raw material sources are extensive, and yield is big, at low cost, easily controllable, is conducive to large-scale industrial production, and the anode material for lithium-ion batteries of preparation has excellent rate charge-discharge performance and excellent service life cycle.

Description

The preparation method of multielement codope LiMn2O4 composite material
Technical field
The invention belongs to technical field of new energy material preparation, it is related to a kind of multielement codope LiMn2O4 composite material Preparation method.
Background technology
Lithium ion battery as new energy carrier have operating voltage height, light weight, small, energy density greatly, follow Ring long lifespan and it is environmentally protective the advantages that, be successfully applied to the energy-storage system of portable electronic device.It is commercialized at present Positive electrode used in lithium ion battery is nearly all with LiCoO2Based on.To reduce the cost of material, making full use of large storage capacity, valence The cheap natural resources of lattice, exploitation and production lithium manganate having spinel structure have important meaning as the positive electrode of lithium ion battery Justice.
Spinel-type LiMn2O4Cell positive material as a new generation is with resourceful, nontoxic, energy density is big, nothing Memory effect is easily recycled the advantages that high with open-circuit voltage, is very promising positive electrode.Currently, spinel-type mangaic acid Lithium obtains large-scale commercial applications not yet, is that there is also many urgent problems to be solved because of it.In environment temperature When relatively low, LiMn2O4Performance declines obviously, reduces the external environment condition that it can be used.Due to Mn's in cyclic process Dissolving is corroded and the dissolving of Jahn-Teller effect and electrolyte causes its capacity attenuation ratio more serious, and cycle life is short.Cause This, to that can be widely used in the positive electrode of lithium ion battery, should put forth effort on for lithium manganate having spinel structure material Improve the chemical property of lithium manganate having spinel structure.
It is bulk phase-doped be from intracell improve lithium manganate having spinel structure positive electrode chemical property effective ways it One.The average valence of Mn ions is improved by adulterating some ions (such as Co, Mg, Al, Cr and part rare earth element), it can The very effective generation for preventing battery Jahn-Teller effect in cyclic process, and then the structural stability of material is promoted, this Outside, partly replace Mn by adulterating other metal ions3+Material caused by the dissolving due to Mn can also be effectively prevent to cave in, To improve LiMn2O4Chemical property.Xiang et al. prepares single element Mg doping pure phases using solid-state combustion method LiMn2O4Composite L iMg0.1Mn1.9O4, tested by electrochemical behavior and show that chemical property is bad, initial discharge is held Measure relatively low only 99.3mAh/g (Xiang et al.Rapidsynthesis of high-cycling performance LiMgxMn2-xO4(x≤0.20)cath-odematerials by a low-temperaturesolid-state combustionmethod[J].Electrochim Acta,2014).Yi et al. prepares Al element dopings using coprecipitation LiMn2O4Composite L iAlxMn2-xO4, in contrast to undoped LiMn2O4, there is preferable stable circulation at relatively high temperatures Property, but react more demanding, not high (the X.Yiet al.Elevatedtemperature cyclic of whole discharge capacity performance of LiAlxMn2-xO4microspheres synthesizedvia co-precipitation route [J] .Alloys Compd, 2014).
Invention content
The object of the present invention is to provide a kind of preparation methods of multielement codope LiMn2O4 composite material.
Realizing the technical solution of the object of the invention is：
The preparation method of multielement codope LiMn2O4 composite material, is as follows：
Step 1, a hydronium(ion) lithia and citric acid stirring is soluble in water, form homogeneous solution；
Step 2, four acetate hydrate manganese, ANN aluminium nitrate nonahydrate, four acetate hydrate magnesium, the stirring of four acetate hydrate cobalts are dissolved in water In, it is added dropwise in the solution that step 1 obtains, is uniformly mixed under 50 ± 5 DEG C of stirrings, dropwise addition ammonium hydroxide adjusting pH to 8 ± 1, it is stirred at 80 ± 10 DEG C to there is colloidal sol generation, is dried to obtain xerogel；
Step 3, in air atmosphere by xerogel, ground after 450 ± 10 DEG C of pre-burnings, then in 750 ± 10 DEG C of high-temperature calcinations, Obtain the three-element doped LiMn2O4 composite L iAl of aluminium cobalt magnesium0.02Co0.05Mg0.05Mn1.88O4。
Preferably, in step 1, the ratio between amount of the citric acid and a hydronium(ion) lithia substance is 1:1.02.
Preferably, in step 2, the whipping temp is 50 DEG C.
Preferably, in step 2, the pH is 8.
Preferably, in step 3, the calcined temperature is 450 DEG C, burn-in time 4h, and high-temperature calcination temperature is 750 DEG C, calcination time is 10~12h.
Preferably, in step 3, the heating rate is 5 DEG C/min.
Preferably, in step 3, the high-temperature calcination temperature is 750 DEG C.
Compared with prior art, the present invention has the following advantages：
(1) the LiMn2O4 composite material of three element codope of aluminium cobalt magnesium prepared by the method for the present invention LiAl0.02Co0.05Mg0.05Mn1.88O4In, tri- kinds of elements of Al, Co, Mg occupy 16dMn instead of Mn ions, to stabilize point Spinel structure, it is suppressed that the generation of Jahn-Teller effect improves high rate performance, cycle life and safety；
(2) the LiMn2O4 composite material of three element codope of aluminium cobalt magnesium prepared by the method for the present invention LiAl0.02Co0.05Mg0.05Mn1.88O4Tri compound doping has been carried out, has reached the resultant effect of various unit doping, shows Good high rate performance has higher specific capacity, high rate performance, cycle performance and security performance；
(3) sol-gal process is more easy to carry out relative to common solid phase method, chemical reaction, by solution reaction step, holds Some trace elements are mixed to easy equal and quantitative, realize the Uniform Doped on molecular level, and only need relatively low synthesis temperature, at This is relatively low, is suitble to industrialized production.
Description of the drawings
Fig. 1 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4With pure phase LiMn2O4XRD diagram.
Fig. 2 is pure phase LiMn2O4(a) the three element codope LiMn2O4 of aluminium cobalt magnesium obtained with 750 DEG C of high-temperature calcinations is compound Material LiAl0.02Co0.05Mg0.05Mn1.88O4(b) SEM partial enlarged views.
Fig. 3 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4EDS figure.
Fig. 4 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4、LiAl0.05Co0.05Mg0.05Mn1.85With pure phase LiMn2O4Cycle performance curve graph.
Fig. 5 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4Constant-current discharge curve graph.
Fig. 6 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4With pure phase LiMn2O4High rate performance figure under different current densities.
Specific implementation mode
With reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
(1) preparation of lithium salts, citric acid solution：When preparing solution, by LiOHH2O and monohydrate potassium are in molar ratio It is 1.02:1 is dissolved in 25ml deionized waters, and stirring is until be completely dissolved；
(2) preparation of manganese salt, aluminium salt, cobalt salt, magnesium salts mixed liquor：By four acetate hydrate manganese, ANN aluminium nitrate nonahydrate, four hydrations Magnesium acetate, four acetate hydrate cobalts are dissolved in after weighing in 50ml deionized waters, and magnetic agitation is uniform；
(3) mixing of solution：Under 50 DEG C of continuous magnetic agitations, prepared manganese salt, aluminium salt, cobalt salt, magnesium salts are mixed Liquid is slowly added dropwise in the mixed solution of lithium salts, citric acid, and after magnetic agitation 10min, the pH that mixed liquor is adjusted with ammonium hydroxide is 8；
(4) preparation of colloidal sol, xerogel：Above-mentioned mixed liquor colloidal sol has been stirred continuously for 80 DEG C on magnetic force heating stirrer It generates, gained colloidal sol is then dried to obtain xerogel；
(5) high temperature sintering：By xerogel at 450 DEG C pre-burning 4h, then grind and calcine 10h under uniform 750 DEG C of high temperature, i.e., Obtain the composite L iAl of three element codope LiMn2O4 of aluminium cobalt magnesium0.02Co0.05Mg0.05Mn1.88O4。
The composite material each element content of 1 aluminium cobalt magnesium of table, three element codope LiMn2O4
Fig. 1 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4With pure phase LiMn2O4XRD diagram, it is known that each diffraction maximum of dopant material with parent spinelle LiMn2O4Diffraction maximum is completely the same, space group Fd3m, and lithium ion occupies 8a, tetrahedron, and manganese atom occupies octahedral 16d.Do not occur the diffraction maximum of doping metals Al, Co, Mg oxide, they completely into the lattice of spinelle, take For the manganese atom on the positions 16d of part, compound is good solid solution after this shows doping.
Fig. 2 is pure phase LiMn2O4(a) the three element codope LiMn2O4 of aluminium cobalt magnesium obtained with 750 DEG C of high-temperature calcinations is compound Material LiAl0.02Co0.05Mg0.05Mn1.88O4(b) SEM schemes, as seen from the figure undoped pure phase LiMn2O4Particle size It is unevenly distributed, and the composite particles that three element codope LiMn2O4 of aluminium cobalt magnesium obtains are evenly distributed, average grain diameter is smaller, With preferable crystallinity.
Fig. 3 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4With pure phase LiMn2O4EDS spectrograms.Table 1 is corresponding each element content table.By Fig. 3 and Table 1 is it is found that there is three kinds of doped chemicals Al, Co, Mg in composite material.
Fig. 4 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4、LiAl0.05Co0.05Mg0.05Mn1.85O4With pure phase LiMn2O4Cycle performance curve graph. As shown in figure 4, the composite L iAl of three element codope LiMn2O4 of aluminium cobalt magnesium0.02Co0.05Mg0.05Mn1.88O4With preferable Cyclical stability, first discharge specific capacity 130mAh/g is higher than single element adulterated lithium manganate, and capacity after recycling 100 times Conservation rate is up to 94%.Composite L iAl0.05Co0.05Mg0.05Mn1.85O4Though first discharge specific capacity there is not, pure phase LiMn2O4 is high, But its capacity retention ratio can reach 84%.In contrast, although the more a height of 134mAh/g of pure phase LiMn2O4 first discharge specific capacity, But capacity attenuation is especially fast, and capacity retention ratio is especially low, is mainly made by the dissolving of Jahn-Teller effect, manganese ion and electrolyte At.Therefore, three element codope LiMn2O4 of aluminium cobalt magnesium improves the structural stability of material to improve following for LiMn2O4 Ring stability.
Fig. 5 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4Constant-current discharge curve graph.Current density is 0.1C, cycle-index 100 in test process It is secondary, obtain for the first time, the 25th time, the 50th time and the 100th constant-current discharge curve.It can be clearly seen that three elements are co-doped with from figure The composite material of miscellaneous LiMn2O4 has a higher capacity retention ratio, and after cycle 100 times, the specific capacity of electric discharge remains at higher Level illustrates good cycling stability.For pure phase LiMn2O4 discharge curve, there are two apparent electric discharges in Fig. 5 Platform is since the presence of doped chemical inhibits λ-MnO2And Li0.5Mn2O4Two-phase coexists.
Fig. 6 is the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that 750 DEG C of high-temperature calcinations obtain LiAl0.02Co0.05Mg0.05Mn1.88O4With pure phase LiMn2O4High rate performance figure under different current densities.Selection 0.1C, The current density of 0.2C, 0.5C, 1.0C, 2.0C carry out high rate performance test experiments, are gradually increased by low current, by 2.0C's After high current, it is gradually reduced electric current, is restored to initial low current, sees the recovery of its capacity, investigates the forthright again of material Energy.Each current density loop test 10 times, obtains that the results are shown in Figure 6.As seen from the figure, with the increase of current density, than Capacity is reducing, and the composite material for the three element codope LiMn2O4 of aluminium cobalt magnesium that high-temperature calcination obtains LiAl0.02Co0.05Mg0.05Mn1.88O4Capacity retention ratio is all higher than pure phase LiMn2O4 when being recycled under different current densities, in electric current Specific capacity does not almost decline when density is restored to 0.1C, shows preferable multiplying power property.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, uniquely the difference is that in the mixed process of (3) solution, whipping temp It is 45 DEG C, is 50 DEG C of sample chemical properties prepared almost indifference with whipping temp, only needs mixing time longer A bit.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, uniquely the difference is that in the mixed process of (3) solution, whipping temp It is 55 DEG C, is 50 DEG C of sample chemical properties prepared almost indifference with whipping temp, and mixing time is close.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, uniquely the difference is that in the mixed process of (3) solution, with ammonium hydroxide tune The pH for saving solution is respectively 7,9, and the chemical property of resulting materials almost indifference when with the pH of solution being 8, the pH of solution is 8 When resulting materials have more preferable crystallinity.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, it is unique unlike (4) colloidal sol, xerogel preparation process in, Mixed liquor is stirred heating respectively at 70 DEG C, 90 DEG C, the sample chemical property prepared with 80 DEG C almost indifference, 80 Agitating and heating is best at DEG C, and the reaction time is shorter, and mixing is more uniform.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, unique the difference is that distinguishing xerogel in (5) high-temperature sintering process The pre-burning at 440 DEG C, 460 DEG C, the sample chemical property prepared with 450 DEG C almost indifference, the pre-burning obtained at 450 DEG C Product particles are more uniform.
Embodiment 7
The present embodiment is substantially the same manner as Example 1, uniquely the difference is that using 740 DEG C in (5) high-temperature sintering process, It is calcined at 760 DEG C, as calcination temperature increases, prepared material crystalline degree is also continuously improved, and is prepared with 750 DEG C Sample chemical property almost indifference.
Comparative example 1
This comparative example is substantially the same manner as Example 1, unique the difference is that using at 800 DEG C in (5) high-temperature sintering process It is calcined.But 800 DEG C of temperature highers lead to serious powder reuniting, and energy consumption is big under conditions of 800 DEG C.
Comparative example 2
Single element Al, Co composite L iAl that adulterated lithium manganate obtains respectively0.02Mn1.98O4And LiCo0.05Mn1.95O4 When current density is 0.1C after cycle 100 times, capacity retention ratio only has 80% and 82%, when single element Mg adulterated lithium manganates for the first time The relatively low only 119mAh/g of discharge capacity, and three element als, Co, Mg codope LiMn2O4Composite material LiAl0.02Co0.05Mg0.05Mn1.88O4First discharge specific capacity is 130mAh/g, and capacity retention ratio is up to 94% after recycling 100 times. Therefore, three element als, Co, Mg codope LiMn2O4Composite L iAl0.02Co0.05Mg0.05Mn1.88O4Relative to single element Al, Co, Mg adulterate LiMn respectively2O4Obtained composite material has preferable cyclical stability and multiplying power property.
Comparative example 3
The LiMn2O4 composite material of three element codope of aluminium cobalt magnesium has preferable cyclical stability and high rate performance.Change The composite L iAl that the content of one of which element al is doped0.05Co0.05Mg0.05Mn1.88O4Carry out electrochemistry It can test, as shown in figure 4, after recycling 100 times, capacity retention ratio only has 84%, and therefore, cyclical stability does not have LiAl0.02Co0.05Mg0.05Mn1.88O4It is good.

Claims (8)

1. the preparation method of multielement codope LiMn2O4 composite material, which is characterized in that be as follows：
Step 1, a hydronium(ion) lithia and citric acid stirring is soluble in water, form homogeneous solution；
It is step 2, four acetate hydrate manganese, ANN aluminium nitrate nonahydrate, four acetate hydrate magnesium, the stirring of four acetate hydrate cobalts is soluble in water, It is added dropwise in the solution that step 1 obtains, is uniformly mixed under 50 ± 5 DEG C of stirrings, ammonium hydroxide is added dropwise and adjusts pH to 8 ± 1, It is stirred at 80 ± 10 DEG C to there is colloidal sol generation, is dried to obtain xerogel；
Step 3, in air atmosphere by xerogel, grind after 450 ± 10 DEG C of pre-burnings, then in 750 ± 10 DEG C of high-temperature calcinations, obtain The three-element doped LiMn2O4 composite L iAl of aluminium cobalt magnesium0.02Co0.05Mg0.05Mn1.88O4。
2. preparation method according to claim 1, which is characterized in that in step 1, the citric acid and a hydrated hydroxide It is 1 to change the ratio between amount of lithium substance:1.02.
3. preparation method according to claim 1, which is characterized in that in step 2, the whipping temp is 50 DEG C.
4. preparation method according to claim 1, which is characterized in that in step 2, the pH is 8.
5. preparation method according to claim 1, which is characterized in that in step 3, the calcined temperature is 450 DEG C, in advance The burning time is 4h, and high-temperature calcination temperature is 750 DEG C, and calcination time is 10~12h.
6. preparation method according to claim 1, which is characterized in that in step 3, the heating rate is 5 DEG C/min.
7. preparation method according to claim 1, which is characterized in that in step 3, the high-temperature calcination temperature is 750 ℃。
8. multielement codope LiMn2O4 composite material made from preparation method according to any one of claims 1 to 7.
CN201810296171.1A 2018-04-04 2018-04-04 The preparation method of multielement codope LiMn2O4 composite material Pending CN108539159A (en)

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CN109192926A (en) * 2018-10-09 2019-01-11 宁波蒙曼生物科技有限公司 A kind of lithium manganate cell positive electrode and its preparation method and application
CN109411731A (en) * 2018-10-31 2019-03-01 云南民族大学 A kind of preparation method of the composite mixed manganate cathode material for lithium of high magnification nickel magnesium
CN110627128A (en) * 2019-09-11 2019-12-31 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material, preparation method and application
CN114420904A (en) * 2021-12-29 2022-04-29 无锡晶石新型能源股份有限公司 Production method of modified lithium manganate material

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CN104253265A (en) * 2013-06-28 2014-12-31 江南大学 Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof
CN104538618A (en) * 2014-12-22 2015-04-22 东北大学 Method for synthesizing monocrystalline-like spinel lithium manganese with high-temperature cyclic stability for lithium battery
CN107316998A (en) * 2017-05-31 2017-11-03 华南理工大学 A kind of long-life LiMn2O4 base anode material of specific composition and shape characteristic and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109192926A (en) * 2018-10-09 2019-01-11 宁波蒙曼生物科技有限公司 A kind of lithium manganate cell positive electrode and its preparation method and application
CN109411731A (en) * 2018-10-31 2019-03-01 云南民族大学 A kind of preparation method of the composite mixed manganate cathode material for lithium of high magnification nickel magnesium
CN110627128A (en) * 2019-09-11 2019-12-31 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material, preparation method and application
CN110627128B (en) * 2019-09-11 2020-11-17 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material, preparation method and application
CN114420904A (en) * 2021-12-29 2022-04-29 无锡晶石新型能源股份有限公司 Production method of modified lithium manganate material

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