CN106410170A - Composite lithium ion battery positive material, and preparation method and lithium ion battery thereof - Google Patents

Composite lithium ion battery positive material, and preparation method and lithium ion battery thereof Download PDF

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CN106410170A
CN106410170A CN201611122316.3A CN201611122316A CN106410170A CN 106410170 A CN106410170 A CN 106410170A CN 201611122316 A CN201611122316 A CN 201611122316A CN 106410170 A CN106410170 A CN 106410170A
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ion battery
lithium ion
preparation
anode material
compound
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CN106410170B (en
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刘立君
宋翠环
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Shenzhen Xin Yongfeng Science And Technology Co Ltd
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Shenzhen Xin Yongfeng Science And Technology Co Ltd
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/50—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a composite lithium ion battery positive material, and a preparation method and a lithium ion battery thereof. The preparation method comprises the following steps: preparing a solution according to a molar ratio of Ni:Co:Mn of X:Y:Z, and carrying out co-precipitation to prepare a precursor oxide, wherein X + Y + Z = 1; preparing a Li source and a precursor oxide; uniformly mixing above materials, and sintering the mixed materials at a high temperature to obtain a lithium-rich ternary material; proportioning the lithium-rich ternary material and MnO2 according to a certain molar ratio, uniformly mixing the lithium-rich ternary material and MnO2 in a solvent, drying the obtained solution, and uniformly grinding the dried solution to obtain mixed powder; sintering the mixed powder at a high temperature; and cooling the sintered mixed powder in a furnace in order to obtain the composite lithium ion battery positive material. A composite system of the ternary material and lithium manganate effectively improves the contact interface of the composite material, makes the composite material well show the synergism, improves the safety and the electrochemical performances of the lithium ion battery and reduces the material cost.

Description

Anode material for compound lithium ion battery and preparation method thereof and lithium ion battery
Technical field
The present invention relates to field of lithium ion battery, more particularly, to a kind of anode material for compound lithium ion battery and its preparation side Method and lithium ion battery.
Background technology
The main flow positive electrode of current driving force lithium ion battery is cobalt nickel lithium manganate ternary material, LiFePO4 etc., ternary Material power lithium-ion battery, compared with lithium iron phosphate power lithium ion battery, has the advantage of its own, and its energy density is high, follows Ring performance is good；And because unit mass carried charge is high, complete vehicle weight declines, course continuation mileage also just accordingly improves.
But ternary material heat stability is poor, under 200 DEG C about of ambient temperature, will decompose and discharge oxygen, Together with the flammable electrolyte in battery, material with carbon element, the heat of generation can be further exacerbated by the decomposition of positive pole, causes that " heat is lost Control ", within the extremely short time will detonation, there is larger security risk.In the choice with performance for the safety, prior art is many Using mixing material system, to balance safety and the performance of lithium ion battery, conventional is by ternary material and LiFePO4, manganese Sour lithium is made into mixing material system according to mass ratio, but the mixing of this physical property is limited to the performance improvement of material.
Therefore, prior art has yet to be improved and developed.
Content of the invention
A kind of in view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide anode material for compound lithium ion battery And preparation method thereof with lithium ion battery it is intended to solve the mixing material that is made into LiFePO4, LiMn2O4 of existing ternary material System, the problem limited to the performance improvement of material.
Technical scheme is as follows：
A kind of preparation method of anode material for compound lithium ion battery, wherein, including step：
A, according to Ni:Co:Mn mol ratio is X:Y:Z is configured to solution, and then presoma oxygen is prepared in co-precipitation in the basic conditions Compound, wherein, X+Y+Z=1；According to 1:1< MLi：（MNi+ MCo+ MMn）≤2:1 proportioning prepares Li source and oxidation of precursor thing, Wherein, M is molal quantity；
After B, above-mentioned material mix homogeneously, sinter 6～8h at a temperature of 600～700 DEG C, obtain rich lithium ternary material；
C, by rich lithium ternary material and MnO2Prepare according to certain mol ratio, wherein MnO2Molal quantity be 2n, n=MLi- （MNi+ MCo+ MMn）, 0<N≤1, and mix homogeneously in a solvent, grind uniformly after being dried, obtain mixed powder；
D, above-mentioned mixed powder is sintered at a temperature of 750～850 DEG C 8～15h；
E, furnace cooling, obtain final product anode material for compound lithium ion battery LiNiXCoYMnZO2/nLiMn2O4, wherein, X+Y+Z=1；0< n≤1.
The preparation method of described anode material for compound lithium ion battery, wherein, in step A, described Ni:Co:Mn mole Than for X:Y:Z=1:1:1、X:Y:Z=8:1:1、X:Y:Z=5:2:One of 3.
The preparation method of described anode material for compound lithium ion battery, wherein, in step A, alkalescence condition refers to pH value and exists Between 10～12.
The preparation method of described anode material for compound lithium ion battery, wherein, in step A, described Li source be lithium carbonate, One of Lithium hydrate.
The preparation method of described anode material for compound lithium ion battery, wherein, in step A, MLi：（MNi+ MCo+ MMn）= 1.3:1.
The preparation method of described anode material for compound lithium ion battery, wherein, in step B, sinters at a temperature of 650 DEG C 7h.
The preparation method of described anode material for compound lithium ion battery, wherein, in step C, n=0.3.
A kind of anode material for compound lithium ion battery, wherein, using as above arbitrary described compound potassium ion battery plus plate The preparation method of material is prepared from；Described anode material for compound lithium ion battery is LiNiXCoYMnZO2/nLiMn2O4, wherein, X+Y+Z=1；0<n≤1.
A kind of lithium ion battery, wherein, including positive pole, negative pole and electrolyte, described positive pole adopts complex lithium as described above Ion battery positive electrode, binding agent and conductive agent are prepared from.
Described lithium ion battery, wherein, the quality of described anode material for compound lithium ion battery, binding agent and conductive agent Ratio is 85-95:2-10:2-10.
Beneficial effect：The ternary material of the present invention and the compound system of LiMn2O4, effectively improve the contact of Material cladding Interface, preferably plays the synergism of composite, improves safety and the chemical property of lithium ion battery, drops simultaneously Low material cost.
Specific embodiment
The present invention provides a kind of anode material for compound lithium ion battery and preparation method thereof and lithium ion battery, for making this Bright purpose, technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that herein Described specific embodiment only in order to explain the present invention, is not intended to limit the present invention.
A kind of preparation method preferred embodiment of anode material for compound lithium ion battery of the present invention, wherein, including step：
A, according to Ni:Co:Mn mol ratio is X:Y:Z is configured to solution, and then presoma oxygen is prepared in co-precipitation in the basic conditions Compound, wherein, X+Y+Z=1；According to 1:1< MLi：（MNi+ MCo+ MMn）≤2:1 proportioning prepares Li source and oxidation of precursor thing, Wherein, M is molal quantity；
Above-mentioned steps A are specifically, according to Ni:Co:Mn mol ratio is X:Y:Z is configured to solution, then coprecipitated in the basic conditions Form sediment preparation oxidation of precursor thing, wherein, X+Y+Z=1；Then according to 1:1< MLi：（MNi+ MCo+ MMn）≤2:1 proportioning is prepared Li source and oxidation of precursor thing, wherein, M is molal quantity.
In step A, described Ni:Co:Mn mol ratio is X:Y:Z=1:1:1、X:Y:Z=8:1:1、X:Y:Z=5:2:In 3 one Kind.Preferably, X:Y:Z=5:2:3.
Described alkalescence condition refers to pH value between 10～12.Preferably, described pH value is 11.
Described lithium source can be but be not limited to one of lithium carbonate, Lithium hydrate.Preferably, described lithium source is hydroxide Lithium.
Preferably, described MLi：（MNi+ MCo+ MMn）=1.3:1.
After B, above-mentioned material mix homogeneously, sinter 6～8h at a temperature of 600～700 DEG C, obtain rich lithium ternary material；Preferably Ground, sinters 7h at a temperature of 650 DEG C.
C, by rich lithium ternary material and MnO2Prepare according to certain mol ratio, wherein MnO2Molal quantity be 2n, n=MLi -（MNi+ MCo+ MMn）, 0<N≤1, and in solvent（As ethanol）Middle mix homogeneously, grinds uniformly after being dried, obtains mixed powder； Preferably, n=0.3.
D, above-mentioned mixed powder is sintered at a temperature of 750～850 DEG C 8～15h；
Above-mentioned steps D, specifically, loading in corundum boat above-mentioned mixed powder, sinter 8～15h under 750～850 DEG C of high temperature. Preferably sintering condition is 780 DEG C of high temperature sintering 12h.
E, furnace cooling, obtain final product anode material for compound lithium ion battery LiNiXCoYMnZO2/nLiMn2O4, wherein, X+Y+Z= 1；0<n≤1.
Due to the poor safety performance of tertiary cathode material, the application in electrokinetic cell field is limited.The present invention passes through Continue the mode of growth at interface, is prepared for the compound system of ternary material and LiMn2O4, effectively improves the contact of Material cladding Interface, preferably plays the synergism of composite, improves safety and the chemical property of lithium ion battery, drops simultaneously Low material cost.
A kind of anode material for compound lithium ion battery of the present invention, wherein, using as above arbitrary described compound lithium ion The preparation method of cell positive material is prepared from；Described anode material for compound lithium ion battery is LiNiXCoYMnZO2/ nLiMn2O4, wherein, X+Y+Z=1；0<N≤1 is it is preferable that n value is 0.3.
A kind of lithium ion battery of the present invention, wherein, including positive pole, negative pole and electrolyte, described positive pole is using as above institute State anode material for compound lithium ion battery, binding agent and conductive agent to be prepared from.
The mass ratio of described anode material for compound lithium ion battery, binding agent and conductive agent is 85-95:2-10:2-10, Preferably mass ratio is 93: 3:4.
Preferably, described binding agent can be PVDF, and described conductive agent can be acetylene black.
The preparation process of positive pole of the present invention is as follows：By anode material for compound lithium ion battery, binding agent（As PVDF）With lead Electric agent（As acetylene black）Example 85-95 in mass ratio:2-10:2-10 is in solvent（As N-Methyl pyrrolidone）In be sufficiently mixed all Even, gained slurry after mix homogeneously is applied on aluminium foil, 120 DEG C of vacuum drying remove solvent and moisture, and pole piece is cut into circle Electrode is as positive pole（I.e. working electrode）.
The preparation process of lithium ion battery of the present invention is as follows：In the glove box full of argon, using metal lithium sheet as right Electrode, Celgard 2400 is barrier film, the LiPF of 1mol/L6/EC-EMC-DMC（Volume ratio is 1:1:1）For electrolyte, assemble Become button cell, stand 4-10h（As 8h）；In 3.0～4.8V voltage range, carry out electrochemical property test.
Compared with prior art, the present invention has following advantage：
（1）Achieve to ternary material LiNiXCoYMnZO2Carry out LiMn2O4Layer cladding is it is suppressed that ternary material and electrolyte Directly contact, it is suppressed that high-temperature catalytic decomposition reaction to electrolyte, not only increases material for the safety of lithium ion battery Property, and improve battery high-temperature behavior, cycle performance.
（2）LiMn2O4Layer is continued growth by the surface in rich lithium ternary material, enhances the conjugation of storeroom, reduction Interfacial effect in composite battery charge and discharge use, the performance increasing composite optimizes synergism.
Below by embodiment, the present invention is described in detail.
Embodiment 1
According to Ni:Co:Mn mol ratio is 1/3:1/3:1/3 preparation solution, co-precipitation preparation oxidation of precursor under the conditions of pH=10 Thing.According to MLi：（MNi+ MCo+ MMn）=2:1 proportioning lithium source and oxidation of precursor thing, after mix homogeneously, 600 DEG C of high temperature sintering 8h, The rich lithium ternary material of synthesis.By rich lithium ternary material and MnO2According to molar ratio 1:2 proportionings, mix all in ethanol medium Even, grind uniformly after being dried, obtain mixed powder.Above-mentioned mixed powder is loaded in corundum boat, 850 DEG C of high temperature sintering 8h；With Stove cools down, and obtains final product anode material for compound lithium ion battery LiNi1/3Co1/3Mn1/3O2/LiMn2O4.
Electrochemical property test：By above-mentioned anode material for compound lithium ion battery, binding agent PVDF and conductive agent acetylene black By 93:3:4 ratio is sufficiently mixed uniformly in solvent N-methyl pyrilidone, and gained slurry is applied on aluminium foil, and 120 DEG C true Empty drying removes solvent and moisture, pole piece is cut into circular electrode as positive pole.In the glove box full of argon, with lithium metal As to electrode, Celgard 2400 is barrier film to piece, the LiPF of 1mol/L6/EC-EMC-DMC（Volume ratio is 1:1:1）For electricity Solution liquid, is assembled into button cell, stands 8h.In 3.0～4.8V voltage range, discharge capacity is 126.9mAh/g to 1C first； Conventional 1C circulates 500 times, and capability retention is 91.8%.
Full electro acupuncture safety experiment result：Pierce through, burn.
Embodiment 2
According to Ni:Co:Mn mol ratio is 0.5:0.2:0.3 preparation solution, co-precipitation preparation oxidation of precursor under the conditions of pH=11 Thing.According to pH=1.3:1 proportioning lithium source and oxidation of precursor thing, after mix homogeneously, 650 DEG C of high temperature sintering 7h, the rich lithium ternary of synthesis Material.By rich lithium ternary material and MnO2According to molar ratio 1:0.6 proportioning, mix homogeneously in ethanol medium, grinds after being dried Mill uniformly, obtains mixed powder.Above-mentioned mixed powder is loaded in corundum boat, 780 DEG C of high temperature sintering 12h；Furnace cooling, obtains final product Composite L iNi0.5Co0.2Mn0.3O2/0.3LiMn2O4.
Battery manufacturing conditions are removed composite, binding agent PVDF and conductive agent acetylene black and are pressed 93:3:4 ratio mixing, its His preparation condition is with embodiment 1；Electrochemical property test condition is also with embodiment 1.Electrochemical property test result：1C is put first Capacitance is 143.6mAh/g；Conventional 1C circulates 500 times, and capability retention is 93.7%.
Full electro acupuncture safety experiment result：Pierce through, burn.
Embodiment 3
According to Ni:Co:Mn mol ratio is 0.8:0.1:0.1 preparation solution, co-precipitation preparation oxidation of precursor under the conditions of pH=12 Thing.According to MLi：（MNi+ MCo+ MMn）=1.5:1 proportioning lithium source and oxidation of precursor thing, after mix homogeneously, 600 DEG C of high temperature sinterings 8h, the rich lithium ternary material of synthesis.By rich lithium ternary material and MnO2According to molar ratio 1:1 proportioning, mixes in ethanol medium Uniformly, grind uniformly after being dried, obtain mixed powder.Above-mentioned mixed powder is loaded in corundum boat, 850 DEG C of high temperature sintering 8h； Furnace cooling, obtains final product anode material for compound lithium ion battery LiNi0.8Co0.1Mn0.1O2/0.5LiMn2O4.
Battery manufacturing conditions are removed composite, binding agent PVDF and conductive agent acetylene black and are pressed 93:3:4 ratio mixing, its His preparation condition is with embodiment 1；Electrochemical property test condition is also with embodiment 1.Electrochemical property test result：1C is put first Capacitance is 145.9mAh/g；Conventional 1C circulates 500 times, and capability retention is 87.3%.
Full electro acupuncture safety experiment result：Pierce through, non-catching fire.
Comparative example 1
It is ternary nickel cobalt manganese 111 material and LiMn2O4 1 that battery manufacturing conditions remove positive electrode active materials:1 molar ratio physical mixing is outer, Other preparation conditions of battery, performance test conditions are with embodiment 1.Electrochemical property test result：Discharge capacity is 1C first 123mAh/g；Conventional 1C circulates 500 times, and capability retention is 83.9%.
Full electro acupuncture safety experiment result：Pierce through, cells burst.
Comparative example 2
It is ternary nickel cobalt manganese 523 material and LiMn2O4 1 that battery manufacturing conditions remove positive electrode active materials:0.3 molar ratio physical mixing Outward, other preparation conditions of battery, performance test conditions are with embodiment 2.Electrochemical property test result：1C discharge capacity first For 140.6mAh/g；Conventional 1C circulates 500 times, and capability retention is 90.4%.
Full electro acupuncture safety experiment result：Pierce through, cells burst
Comparative example 3
It is ternary nickel cobalt manganese 811 material and LiMn2O4 1 that battery manufacturing conditions remove positive electrode active materials:0.5 molar ratio physical mixing Outward, other preparation conditions of battery, performance test conditions are with embodiment 3.Electrochemical property test result：1C discharge capacity first For 139.7mAh/g；Conventional 1C circulates 500 times, and capability retention is 81.5%.
Full electro acupuncture safety experiment result：Pierce through, swift and violent detonation.
In sum, present invention achieves to ternary material LiNiXCoYMnZO2Carry out LiMn2O4Layer cladding is it is suppressed that three The directly contact of first material and electrolyte, it is suppressed that high-temperature catalytic decomposition reaction to electrolyte, not only increases material and is used for The safety of lithium ion battery, and improve battery high-temperature behavior, cycle performance.In addition, LiMn2O4Layer is by rich lithium ternary Continue growth on the surface of material, enhances the conjugation of storeroom, reduces the interfacial effect during composite battery charge and discharge uses, The performance increasing composite optimizes synergism.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention Shield scope.

Claims (10)

1. a kind of preparation method of anode material for compound lithium ion battery is it is characterised in that include step：
A, according to Ni:Co:Mn mol ratio is X:Y:Z is configured to solution, and then presoma oxygen is prepared in co-precipitation in the basic conditions Compound, wherein, X+Y+Z=1；According to 1:1<MLi：（MNi+ MCo+ MMn）≤2:1 proportioning prepares Li source and oxidation of precursor thing, Wherein, M is molal quantity；
After B, above-mentioned material mix homogeneously, sinter 6～8h at a temperature of 600～700 DEG C, obtain rich lithium ternary material；
C, by rich lithium ternary material and MnO2Prepare according to certain mol ratio, wherein MnO2Molal quantity be 2n, n=MLi- （MNi+ MCo+ MMn）, 0<N≤1, and mix homogeneously in a solvent, grind uniformly after being dried, obtain mixed powder；
D, above-mentioned mixed powder is sintered at a temperature of 750～850 DEG C 8～15h；
E, furnace cooling, obtain final product anode material for compound lithium ion battery LiNiXCoYMnZO2/nLiMn2O4, wherein, X+Y+Z=1；0< n≤1.
2. the preparation method of anode material for compound lithium ion battery according to claim 1 is it is characterised in that in step A, Described Ni:Co:Mn mol ratio is X:Y:Z=1:1:1、X:Y:Z=8:1:1、X:Y:Z=5:2:One of 3.
3. the preparation method of anode material for compound lithium ion battery according to claim 1 is it is characterised in that in step A, Alkalescence condition refers to pH value between 10～12.
4. the preparation method of anode material for compound lithium ion battery according to claim 1 is it is characterised in that in step A, Described Li source is one of lithium carbonate, Lithium hydrate.
5. the preparation method of anode material for compound lithium ion battery according to claim 1 is it is characterised in that in step A, MLi：（MNi+ MCo+ MMn）=1.3:1.
6. the preparation method of anode material for compound lithium ion battery according to claim 1 is it is characterised in that in step B, 7h is sintered at a temperature of 650 DEG C.
7. the preparation method of anode material for compound lithium ion battery according to claim 1 is it is characterised in that in step C, n=0.3.
8. a kind of anode material for compound lithium ion battery is it is characterised in that adopt described complex lithium as arbitrary in claim 1 ~ 7 The preparation method of ion battery positive electrode is prepared from；Described anode material for compound lithium ion battery is LiNiXCoYMnZO2/ nLiMn2O4, wherein, X+Y+Z=1；0<n≤1.
9. a kind of lithium ion battery is it is characterised in that include positive pole, negative pole and electrolyte, described positive pole is using as claim 8 Described anode material for compound lithium ion battery, binding agent and conductive agent are prepared from.
10. lithium ion battery according to claim 9 is it is characterised in that described anode material for compound lithium ion battery, viscous The mass ratio of knot agent and conductive agent is 85-95:2-10:2-10.
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CN109713244A (en) * 2017-10-26 2019-05-03 浙江工业大学 A kind of stratiform ternary richness lithium material of surface-carbon-modified cathode and its application
CN110034293A (en) * 2019-05-08 2019-07-19 福州大学 A kind of LiMn2O4The preparation method of coated lithium ion battery tertiary cathode material
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