CN107834050A - A kind of lithium-enriched cathodic material of lithium ion battery and its improved method - Google Patents

A kind of lithium-enriched cathodic material of lithium ion battery and its improved method Download PDF

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CN107834050A
CN107834050A CN201711323990.2A CN201711323990A CN107834050A CN 107834050 A CN107834050 A CN 107834050A CN 201711323990 A CN201711323990 A CN 201711323990A CN 107834050 A CN107834050 A CN 107834050A
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lithium
positive electrode
covering
ion battery
lithium ion
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张海朗
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Jiangnan University
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Jiangnan University
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    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC 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 present invention relates to a kind of lithium-enriched cathodic material of lithium ion battery and its improved method, belongs to anode material for lithium-ion batteries technical field.It includes positive electrode and three class commodity lithium ion anode covering materials, covering material LiCoO2、LiMn2O4Or LiFePO4.Heat to obtain gel using sol-gal process stirring in water bath, xerogel is obtained after drying, passing through low temperature presintering knot and high-temperature calcination respectively, positive electrode is being obtained after cooling grinding, then by the positive electrode and LiCoO of preparation2And LiMn2O4Covering material is scattered in deionized water, constant temperature stirring, then stands, filters, washs, dries, and it is material modified to obtain lithium ion battery lithium-rich anode through calcining.And LiFePO4Using liquid phase coating method, positive electrode is dispersed in ANN aluminium nitrate nonahydrate solution, constant temperature stirs, and stands, filters, washs, dries, and is obtained after calcining required material modified.Preparation method of the present invention is easy, easy to operate, and the material modified particle size distribution of the lithium-rich anode being prepared is uniform, and crystallinity is high, and material high rate performance and cyclicity are improved significantly after cladding.

Description

A kind of lithium-enriched cathodic material of lithium ion battery and its improved method
Technical field
The present invention relates to a kind of lithium-enriched cathodic material of lithium ion battery and its improved method, belongs to lithium ion cell positive material Expect technical field.
Background technology
Lithium ion battery is as green secondary cell, because of the feature such as its specific capacity is high, power density is big, has extended cycle life It is widely used in all kinds of digital electronic goods and communication apparatus.With the continuous popularization and expansion of its application, lithium-ion electric Pond gradually just comes onto stage in the high capacity cell such as electric automobile market, receives much concern.With regard to the development process of present lithium ion battery For, compared with the lithium ion battery negative material and electrolyte that develop rapidly, the development of positive pole material is relatively slow;And with regard to its big rule For mould is promoted, positive electrode all occupies leading factor in terms of its Cost And Performance.Therefore, cheap, safety is developed The positive electrode of excellent performance is the key for promoting lithium ion battery commercialization to promote.Positive electrode main at present includes: LiCoO2、LiNiO2、LiMn2O4、LiCoO2/LiNiO2/LiMn2O4Ternary eutectic system and height ratio capacity rich lithium solid solution Body system.LiCoO2Stable electrochemical property, but the too late theoretical half of actual capacity, and Co elements are expensive, poisonous, lead Cost is caused can not to be in any more;LiNiO2Specific capacity is high, but synthesis condition is extremely harsh;LiMn2O4Middle promoter manganese enriches, cheap, But phase transformation in cyclic process be present, cyclical stability is poor;Ternary eutectic system has had LiCoO concurrently2、LiNiO2、LiMn2O4Three classes The characteristics of material, obvious three elements cooperative effect, electrochemical performance, but the specific capacity of the system be present still relatively It is low, it is difficult to meet electric automobile to high power capacity, the growth requirement of high-energy-density.In recent years, rich lithium solid solution cathode material because Its specific capacity is high, low-cost clear superiority and turn into study hotspot.
The formula of lithium-rich anode material is xLi2MnO3·(1-x)LiMnO2, such material, which has, is different from traditional positive pole material The charging mechanism of material.When charging voltage is higher than 4.5V, the charging curve of rich lithium material can be one longer in 4.5V or so appearance De- lithium deoxidation platform, correspond to Li2MnO3The activation of structure, structure recombinate, and form more orderly layer structure, so as to So that still there is higher specific discharge capacity in follow-up discharge process.But there is capacity usage ratio first in such material Low, irreversible capacity loss is big, under high current density the problem of high rate performance difference.
The deficiency remained for current lithium-rich anode material, material electrochemical can be improved by surface coating modification Can, the main purpose of cladding is in the stable compound of one layer of chemical property of positive electrode surface attachment, effectively suppresses positive pole Side reaction between active material and electrolyte, while maintaining material surface structural integrity and stablizing also to a certain extent Inhibit the decomposition of electrolyte.At the same time, cladding also advantageously improves material electric conductivity and ionic conductance so that after cladding Material electrochemical performance is more excellent.
The content of the invention
It is an object of the present invention to overcome the above deficiencies, there is provided a kind of lithium-enriched cathodic material of lithium ion battery and its changes Enter method.
According to technical scheme provided by the invention, a kind of lithium-enriched cathodic material of lithium ion battery, including positive electrode and business Product positive electrode material layer, commodity positive electrode material layer are coated on the outer layer of prepared lithium-rich anode material;
Described lithium-rich anode material is Li [Li0.2Ni0.15Mn0.55Co0.1]O2;The covering material is LiCoO2、 LiMn2O4Or LiFePO4, the covering material LiCoO2It is 1-5.5wt% with positive electrode mass ratio, the covering material LiMn2O4Or LiFePO4It is 1-5.5wt% with positive electrode mass ratio.
The preparation method of the lithium-enriched cathodic material of lithium ion battery, step are as follows:
(1) mix:According to lithium:Nickel:Manganese:The mol ratio of cobalt is 1.2~1.35:0.15~0.155:0.55~0.60:0.1 ~0.105 feeding, citric acid is added, the nickel salt, nickel salt, manganese salt and the integral molar quantity of cobalt salt and the mol ratio of citric acid are 1: 1~1.15:1.55;After well mixed, the pH of mixed solution is adjusted to 7~8 with ammoniacal liquor;
(2) heat:Step (1) resulting solution is heated in 70~90 DEG C of stirring in water bath, obtains gelinite;
(3) dry:Gelinite obtained by step (2) is dried 18~30 hours at 100~150 DEG C, obtains xerogel body;
(4) preparation of presoma:Step (3) is prepared into gained xerogel body in 400~600 DEG C of pre-sinterings 5~10 hours, Grinding obtains presoma after naturally cooling to room temperature;
(5) preparation of positive electrode:Precursor powder obtained by step (4) is transferred to crucible, is placed at 800~1000 DEG C and roasts Burn 10~18 hours, be fully ground to obtain positive electrode after cooling;
(6) it is modified:1~5.5wt% covering material LiCoO is added in the positive electrode that step (5) prepares gained2Or LiMn2O4, then mixture is scattered in the solvent of 6~11 times of quality, is stirred vigorously at 40~60 DEG C, makes positive electrode Be uniformly dispersed with covering material, until solvent volatilizees substantially, dry 18~25 hours at 70~100 DEG C, finally 400~ Sinter that to produce lithium ion battery lithium-rich anode within 5~10 hours material modified at 600 DEG C;
Or prepare gained positive electrode and 1-5.5wt% covering material LiFePO in step (5)4It is scattered in 6~11 times The H of quality2In O solution, it is stirred vigorously at 40~60 DEG C, makes positive electrode and covering material LiFePO4It is uniformly dispersed, until Solvent volatilizees substantially, at 70~100 DEG C dry 18~25 hours, finally at 400~60 DEG C sinter 5~10h produce lithium from Sub- battery lithium-rich anode is material modified.
Lithium source in the lithium salts is LiNO3、CH3One or more in COOLi, LiOH;Nickel source in nickel salt is Ni (NO3)2、Ni(CH3COO)2、NiSO4In one or more;Cobalt source in cobalt salt is Co (NO3)2、Co(CH3COO)2、CoSO4 In one or more.
Step (6) described solvent is distilled water or ethanol.
Beneficial effects of the present invention:Preparation method technique of the present invention is simple, easily operated, gained lithium-rich anode material purity Height, particle diameter is small and is evenly distributed, and particle dispersion is good.The presence of covering material inhibits corruption of the electrolyte to surface of active material Erosion and the generation of interface side reaction, so as to maintain the stability of material interface, reduce the impedance in cyclic process, Li+'s Diffusion rate is improved, while remains more lithium rooms and Lacking oxygen, ensures that the smooth deintercalation of lithium ion, bag Cover modification and improve material high rate performance and cycle performance, in addition, covering material sheet does not have bright as lithium ion anode material, capacity It is aobvious to be affected, process costs are reduced, are advantageous to promote the process of commercialization.
Brief description of the drawings
Fig. 1 is the x-ray diffraction pattern of positive electrode prepared by embodiment 1~4.
Fig. 2 is the scanning electron microscope (SEM) photograph of positive electrode prepared by embodiment 1~4.
Fig. 3 is positive electrode prepared by embodiment 1~4, first charge-discharge curve map during normal temperature under 0.2C electric currents, electric discharge Voltage range is 2-4.8V.
Fig. 4 is positive electrode prepared by embodiment 1~4, cyclic curve figure during normal temperature under 0.2C electric currents, charging/discharging voltage Scope is 2-4.8V.
The positive electrode that Fig. 5 is prepared for embodiment 1~4, the cyclic curve figure in normal temperature under different multiplying, discharge and recharge Voltage range is 2-4.8V.
Embodiment
Below in conjunction with specific drawings and Examples, the present invention is further illustrated.
A kind of 1 lithium-enriched cathodic material of lithium ion battery of embodiment is Li [Li0.2Ni0.15Mn0.55Co0.1]O2, including following step Suddenly:
(1) mix:According to stoichiometric proportion (1.26:0.15:0.55:0.1) analytically pure CH is weighed3COOLi·2H2O、 Ni(CH3COO)2·4H2O、Mn(CH3COO)·4H2O、Co(CH3COO)2·4H2O, it is dissolved in deionized water, is gradually added dropwise respectively Citric acid solution, the addition of citric acid solution are equal to the mole sum of transition metal ions, with concentrated ammonia liquor by mixed solution PH value adjust to 7 or so;
(2) heat:The mixed solution system that step (1) is obtained in 80 DEG C of water-bath heating stirring to evaporate moisture, Gradually obtain gelinite;
(3) dry:The gelinite that step (2) is obtained dries 24h in 120 DEG C of air dry ovens, obtains xerogel;
(4) preparation of presoma:Dry gelinite is subjected to pre-burning, calcined temperature is 500 DEG C, and burn-in time is 6 small When, obtain presoma;Ground after being cooled to room temperature;
(5) preparation of positive electrode:Presoma after grinding is subjected to high-temperature calcination, calcination time 12 at 900 DEG C Hour, fully cold rear grinding, that is, obtain positive electrode Li [Li0.2Ni0.15Mn0.55Co0.1]O2
A kind of Surface coating 3wt%LiCoO of embodiment 22Lithium ion battery lithium-rich anode material Li [Li0.2Ni0.15Mn0.55Co0.1]O2, comprise the following steps:
Li [the Li that embodiment 1 is prepared0.2Ni0.15Mn0.55Co0.1]O2Positive electrode and mass fraction ratio are 3wt% LiCoO2It is dispersed in the ethanol solution of 11 times of quality, heating stirring at 40 DEG C, until solvent volatilizees completely substantially, in 80 DEG C of bars Dried 24 hours under part, last 450 DEG C of calcinings 6h obtains final product Surface coating 3wt%LiCoO2Li [Li0.2Ni0.15Mn0.55Co0.1]O2
A kind of Surface coating 3wt%LiMn of embodiment 32O4Lithium ion battery lithium-rich anode material Li [Li0.2Ni0.15Mn0.55Co0.1]O2, comprise the following steps:
Li [the Li that will be prepared0.2Ni0.15Mn0.55Co0.1]O2Positive electrode and mass fraction ratio are respectively 3wt% LiMn2O4It is dispersed in the ethanol solution of 7 times of quality, heating stirring at 40 DEG C, until solvent volatilizees completely substantially, in 80 DEG C of bars Dried 24 hours under part, last 450 DEG C of calcinings 6h obtains final product Surface coating 3wt%LiMn2O4Li [Li0.2Ni0.15Mn0.55Co0.1]O2
A kind of Surface coating 3wt%LiFePO of embodiment 44Lithium-enriched cathodic material of lithium ion battery Li [Li0.2Ni0.15Mn0.55Co0.1]O2, comprise the following steps:
It is 3wt%LiFePO by the positive electrode prepared and mass fraction ratio4It is dispersed in the aqueous solution, is heated at 80 DEG C Stirring, until solvent volatilizees completely substantially, dried 24 hours under the conditions of 90 DEG C, last 450 DEG C of calcinings 6h is finally produced Thing surface is respectively coated by 3wt%LiFePO4Li [Li0.2Ni0.15Mn0.55Co0.1]O2
Application Example 1
XRD diffraction tests are carried out respectively to embodiment 1-4 resulting materials, it is specific as shown in Figure 1;Carry out electron-microscope scanning, tool Body is as shown in Figure 2.
From the XRD diffracting spectrums of embodiment in Fig. 1 1~4, each material has obvious α-NaFeO after cladding2Six sides Crystallographic system layer structure, the impurity peaks for belonging to clad element are not occurred.
Uncoated material particle size is smaller it can be seen from the SEM figures of embodiment in Fig. 2 1~4 and is evenly distributed, particle table It is face flat smooth, clear-cut, and the particle surface of material occurs being individually present or reunited at one piece after coating modification Nanometer little particle, causes material granule to increase, the profile between particle becomes unintelligible, and this shows LiCoO2、LiMn2O4 Or LiFePO4Covering material is successfully coated on material granule surface.
By the positive electrode synthesized in embodiment 1~4 according to m (positive electrode):M (acetylene black):M (PVDF)=80:12: 8 quality is made into underflow material (NMP is solvent) than mixed grinding, using Doctor Blade technologies, is spread evenly across collector On aluminium foil, dried at 80 DEG C, 3MPa is rolled, and is madeAnode pole piece, through 80 DEG C vacuum drying 12 hours after make With.
Using lithium piece as cathode pole piece, (EC+DMC+EMC volume ratios are 1 to 1mol/L LiPF6 solution:1:1) it is electrolyte, Celgard2325 holes film makees barrier film, and use for laboratory button (CR2032) test electricity is assembled into the glove box full of argon gas Pond.Charge-discharge test, discharge and recharge are carried out to the experimental cell assembled using Land test discharge and recharge instrument (Wuhan Jin Nuo companies) Section is 2~4.8V.
Due to the volatilization of Li elements in the building-up process of positive electrode be present, the reduction of Li contents is caused, so as to cause material Expect crystal structure existing defects, therefore the actual mole dosage of lithium salts wants excessive 5%.
From first charge-discharge curve of the positive electrode of Fig. 3 embodiments 1~4 under 2~4.8V and 0.2C, before cladding The initial charge curve of individual each material is respectively provided with the charging platform of two exemplary Home lithium-rich anode materials afterwards.When charging voltage exists Below 4.5V is the redox of transition metal in corresponding material of main part;When charging voltage rises to more than 4.5V, occur one Individual longer and shallower 4.5V platforms, corresponding crystal depth take off lithium and with lattice deoxidation.4.5V platforms are still deposited after cladding Illustrating that cladding does not change the charge-discharge mechanism of material.By figure it can also be seen that the specific discharge capacity of material increases after cladding Greatly, coulombic efficiency is improved first.
Fig. 4 is cycle performance figure of the positive electrode of embodiment 1~4 under 2-4.8V and 0.2C.Material exists in embodiment 1 Capacity decays to 189.1mAh/g by 231.5 after lower 50 circulations of 0.2C current densities, capability retention 86.3%, and 3wt%-LiCoO2, 3wt%-LiMn2O4And 3wt%-LiFePO4Capacity decays to respectively after 50 cycle periods: 219.3mAh/g, 212.1mAh/g and 223.5mAh/g, capability retention are respectively:95.5%th, 90.5% and 96.3%.Explanation Cladding is to improve the effective means of material circulation performance.The presence of clad effectively inhibit electrode active material and electrolyte it Between side reaction, the complete and stability of material interface is maintained, so as to improve the cycle performance of material.
Fig. 5 is high rate performance figure of the positive electrode of embodiment 1~4 under 2-4.8V difference current densities.Embodiment 1, 2nd, first all specific discharge capacity of 3,4 positive electrode under 0.2C is respectively:217.8mAh/g、231.5mAh/g、235.2mAh/ G, 238.3mAh/g, when multiplying power increases to 1C, the specific discharge capacity of each material is respectively:145mAh/g、166.7mAh/g、 165.1mAh/g、178.9mAh/g.It follows that with the continuous increase of multiplying power, difference is presented in the specific discharge capacity of each material The decay of degree, and compared to uncoated material, capacity attenuation speed of the material under different multiplying is retarded after cladding, 1C Under still keep higher specific discharge capacity.Illustrate that cladding can improve the high rate performance of material.
Compared with uncoated positive electrode, pass through LiCoO in embodiment 2~4 in the present invention2、LiMn2O4Or LiFePO4 Covering material is coated to positive electrode so that the initial discharge specific capacity of positive electrode is improved, and cyclical stability obtains Improved to high rate performance, the cladding 3.0wt%LiFePO especially prepared in embodiment 44Li [Li0.2Ni0.15Mn0.55Co0.1]O2Combination property effect it is best.

Claims (4)

1. a kind of improvement of lithium-enriched cathodic material of lithium ion battery, it is characterized in that:Including positive electrode and commodity positive electrode material layer, Commodity positive electrode material layer is coated on the outer layer of the positive electrode of synthesis;
Described positive electrode is Li [Li0.2Ni0.15Mn0.55Co0.1]O2;The covering material is LiCoO2、LiMn2O4Or LiFePO4, the covering material LiCoO2It is 1-5.5wt%, the covering material LiMn with positive electrode mass ratio2O4Or LiFePO4It is 1-6wt% with positive electrode mass ratio.
2. the preparation method of lithium-enriched cathodic material of lithium ion battery described in claim 1, it is characterized in that step is as follows:
(1) mix:According to lithium:Nickel:Manganese:The mol ratio of cobalt is 1.2~1.35:0.15~0.155:0.55~0.60:0.1~ 0.105 feeding, citric acid is added, the nickel salt, nickel salt, manganese salt and the integral molar quantity of cobalt salt and the mol ratio of citric acid are 1:1 ~1.15:1.55;After well mixed, the pH of mixed solution is adjusted to 7~8 with ammoniacal liquor;
(2) heat:Step (1) resulting solution is heated in 70~90 DEG C of stirring in water bath, obtains gelinite;
(3) dry:Gelinite obtained by step (2) is dried 18~30 hours at 100~150 DEG C, obtains xerogel body;
(4) preparation of presoma:Step (3) is prepared into gained xerogel body in 400~600 DEG C of pre-sinterings 5~10 hours, it is natural Grinding obtains presoma after being cooled to room temperature;
(5) preparation of positive electrode:Precursor powder obtained by step (4) is transferred to crucible, is placed at 800~1000 DEG C and is calcined 10 ~18 hours, it is fully ground to obtain positive electrode after cooling;
(6) it is modified:1~5.5wt% covering material LiCoO is added in the positive electrode that step (5) prepares gained2Or LiMn2O4, then mixture is scattered in the solvent of 6~11 times of quality, is stirred vigorously at 40~60 DEG C, makes positive electrode Be uniformly dispersed with covering material, until solvent volatilizees substantially, dry 18~25 hours at 70~100 DEG C, finally 400~ Sinter that to produce lithium ion battery lithium-rich anode within 5~10 hours material modified at 600 DEG C;
Or prepare gained positive electrode and 1-5.5wt% covering material LiFePO in step (5)4It is scattered in 6~11 times of quality H2In O solution, it is stirred vigorously at 40~60 DEG C, makes positive electrode and covering material LiFePO4It is uniformly dispersed, until solvent base This volatilization, dried at 70~100 DEG C 18~25 hours, 5~10h is finally sintered at 400~60 DEG C and produces lithium ion battery Lithium-rich anode is material modified.
3. the material modified preparation method of lithium ion battery lithium-rich anode as claimed in claim 2, it is characterized in that:In the lithium salts Lithium source be LiNO3、CH3One or more in COOLi, LiOH;Nickel source in nickel salt is Ni (NO3)2、Ni(CH3COO)2、 NiSO4In one or more;Cobalt source in cobalt salt is Co (NO3)2、Co(CH3COO)2、CoSO4In one or more.
4. the material modified preparation method of lithium ion battery lithium-rich anode as claimed in claim 2, it is characterized in that:Step (6) institute It is distilled water or ethanol to state solvent.
CN201711323990.2A 2017-12-13 2017-12-13 A kind of lithium-enriched cathodic material of lithium ion battery and its improved method Pending CN107834050A (en)

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CN111082009A (en) * 2019-12-17 2020-04-28 中南大学 Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof
CN111082009B (en) * 2019-12-17 2021-04-09 中南大学 Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof
CN111082029A (en) * 2019-12-31 2020-04-28 北京当升材料科技股份有限公司 Lithium-rich manganese-based material and preparation method and application thereof
WO2021136490A1 (en) * 2019-12-31 2021-07-08 北京当升材料科技股份有限公司 Lithium-rich manganese-based material, preparation method therefor and application thereof
CN111082029B (en) * 2019-12-31 2021-08-03 北京当升材料科技股份有限公司 Lithium-rich manganese-based material and preparation method and application thereof
CN111446444A (en) * 2020-03-03 2020-07-24 北京当升材料科技股份有限公司 Lithium-rich manganese-based material and preparation method and application thereof
CN111446444B (en) * 2020-03-03 2021-06-15 北京当升材料科技股份有限公司 Lithium-rich manganese-based material and preparation method and application thereof
CN112421010A (en) * 2020-11-25 2021-02-26 惠州亿纬锂能股份有限公司 Cathode material, preparation method thereof and lithium ion battery

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Application publication date: 20180323