CN103943841A - Anion doped modified lithium ion battery (4:4:2) type ternary cathode material and preparing method thereof - Google Patents

Anion doped modified lithium ion battery (4:4:2) type ternary cathode material and preparing method thereof Download PDF

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CN103943841A
CN103943841A CN201310023488.5A CN201310023488A CN103943841A CN 103943841 A CN103943841 A CN 103943841A CN 201310023488 A CN201310023488 A CN 201310023488A CN 103943841 A CN103943841 A CN 103943841A
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cathode material
lithium ion
ion battery
salt
gel
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张海朗
杨威
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Jiangnan University
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Jiangnan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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
    • 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 relates to an anion doped modified lithium ion battery (4:4:2) type ternary cathode material and a preparing method thereof, and belongs to the field of lithium ion batteries. The general chemical formula of the cathode material is LiNi<0.4>Co<0.2>Mn<0.4>O<2-z>Xz, wherein the X is F, Cl or Br; and the Z is more than 0 and not more than 0.15. The method includes steps of: weighing a soluble lithium salt, a nickel salt, a manganese slat, a cobalt salt and an X salt according to a molar ratio, dissolving the weighed compounds separately with deionized water, adding a citric acid solution and mixing and stirring uniformly, adjusting the pH value by utilization of concentrated ammonia liquor, heating and evaporating to obtain gel, heating and drying the gel, and performing two times of firing and grinding to obtain the anion doped modified lithium ion battery (4:4:2) type ternary cathode material. Particles of the lithium ion battery cathode material are fine and uniform and reach the nanometer level, so that the cathode material has characteristics of high discharge capacity, excellent cyclic stability and rate capacity, capability of maintaining the properties at high or low temperature conditions, convenience for large-scale industrial production, and high practical degree.

Description

The lithium ion battery of anion doped modification (4:4:2) type tertiary cathode material and preparation method thereof
Technical field
The present invention relates to lithium ion battery (4:4:2) type tertiary cathode material of a kind of anion doped modification and preparation method thereof, belong to lithium ion battery field.
Background technology
At present, along with the development of digital product and electric automobile, the research of high-performance lithium ion rechargeable type secondary cell becomes heat subject.And anode material for lithium-ion batteries is as determining performance of lithium ion battery and the most important link of cost, become especially the focus of people's research.At present, LiCoO 2because it has, operating voltage is high, capacity large, electric discharge is steady, be applicable to the features such as heavy-current discharge and good cycle, becomes most widely used positive electrode in business.But cobalt is rare metal, expensive, environment is had to certain pollution.Therefore, people's study hotspot transfers to cheap, environment amenable other transistion metal compounds and substitutes LiCoO 2material.LiNi xco ymn 1-x-yo 2the comprehensive LiCoO of tertiary cathode material 2, LiNiO 2, LiMn 2o 4the feature of three class materials, thus possess that capacity is high, Stability Analysis of Structures, fail safe is good, low cost and other advantages becomes to become one of positive electrode of commercialization potentiality most.LiNi 1/3mn 1/3co 1/3o 2the tertiary cathode material of current most study, ternary material LiNi 0.4co 0.2mn 0.4o 2with LiNi 1/3mn 1/3co 1/3o 2compare, the content of the Co that it is expensive still less, can reduce the cost of material to a certain extent, reduces the pollution of production process to environment.Ni is maximum to capacity contribution, and the relative increase of Ni content can make material have higher theoretical specific capacity, thereby LiNi 0.4co 0.2mn 0.4o 2it is a kind of tertiary cathode material that has more researching value.And with regard to the requirement of commercial applications, LiNi 0.4co 0.2mn 0.4o 2what positive electrode need to improve is the charging and discharging capabilities of tap density, energy force density, circulation ability and large multiplying power.For current LiNi 0.4co 0.2mn 0.4o 2the deficiency that tertiary cathode material remains, need start with from material being carried out to the aspects such as doping vario-property.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of lithium ion battery (4:4:2) type tertiary cathode material preparation method of nanoscale anionic doping vario-property is provided, this positive electrode particle is little and even, smooth surface, crystal property is good, has capacity high, and coulomb efficiency is high, good cycle under high/low temperature condition, the advantages such as good rate capability.
According to technical scheme provided by the invention, a kind of lithium ion battery of anion doped modification (4:4:2) type tertiary cathode material, the chemical general formula of described positive electrode is LiNi 0.4co 0.2mn 0.4o 2-zx z, X is F, Cl or Br, 0 < Z≤0.15;
According to mol ratio, take solubility lithium salts, nickel salt, manganese salt, cobalt salt, X salt, respectively with after deionized water dissolving, add citric acid solution mixing and stirring, with heating evaporation after concentrated ammonia liquor adjusting pH, obtain gel.After gel heat drying, through twice calcination, grind lithium ion battery (4:4:2) the type tertiary cathode material that obtains the anion doped modification of product.
The lithium ion battery of anion doped modification (4:4:2) type tertiary cathode material, step is as follows:
(1) preparation of gel: according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: Z) take analytically pure lithium salts, nickel salt, cobalt salt, manganese salt, X salt, be dissolved in respectively in deionized water, add citric acid solution, addition equals the mole sum of transition metal ions, mixing and stirring, regulates pH value to 7-8 with concentrated ammonia liquor, 60-100 ℃ of heating water bath evaporation, and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel dry 8-15 hour at 80-150 ℃ prepared by step (1), process 4-8 hour and be placed on 300-600 ℃ of pre-calcination; Naturally cool to grinding at room temperature and obtain presoma; Powder after grinding is placed in roasting 10-20 hour under 700-1000 ℃ of condition, and lithium ion battery (4:4:2) the type tertiary cathode material that obtains the anion doped modification of product is ground in cooling rear continuation.
Further, described lithium salts is LiNO 3, CH 3one or more in COOLi, LiOH, described nickel salt is Ni (NO 3) 2, Ni (CH 3cOO) 2, NiSO 4in one or more, described manganese salt is Mn (NO 3) 2, Mn (CH 3cOO) 2, MnSO 4in one or more, described cobalt salt is Co (NO 3) 2, Co (CH 3cOO) 2, CoSO 4in one or more, described X salt is a kind of in LiCl, LiF, LiBr.
Tool of the present invention has the following advantages:
(1) the prepared positive electrode particle diameter of the present invention is evenly distributed, and degree of crystallinity is high, smooth surface, particle good dispersion degree;
(2) positive electrode provided by the present invention, due to the doping vario-property of anion, material structure is more stable.Thereby make all to possess under material high/low temperature condition cycle performance and the high rate performance of higher discharge capacity, excellence.And the required cost of material of doping vario-property is cheap, has further reduced positive electrode and has produced required cost, is conducive to advance commercial process.
Accompanying drawing explanation
Fig. 1 is the positive electrode LiNi of comparative example and embodiment 2 preparations 0.4co 0.2mn 0.4o 1.95cl 0.05x-ray diffraction pattern.
Fig. 2 is the positive electrode LiNi of embodiment 2 preparations 0.4co 0.2mn 0.4o 1.95cl 0.05scanning electron microscope (SEM) photograph.
Fig. 3 is the positive electrode of comparative example and embodiment 1-3, cyclic curve figure during normal temperature under 0.2C electric current, and charging/discharging voltage scope is 2.0-4.6V.
Fig. 4 is the positive electrode of comparative example and embodiment 1-3, the cyclic curve figure in the time of 55 ℃ under 0.2C electric current, and charging/discharging voltage scope is 2.0-4.6V.
Fig. 5 is the positive electrode of comparative example and embodiment 2,4,6, the cyclic curve figure in the time of 55 ℃ under 0.2C electric current, and charging/discharging voltage scope is 2.0-4.6V.
Fig. 6 is the positive electrode of comparative example and embodiment 4, the cyclic curve figure when normal temperature under different multiplying, and charging/discharging voltage scope is 2.0-4.6V.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but embodiments of the present invention are not limited to this.
Comparative example is Li doped Ni not 0.4co 0.2mn 0.4o 2the preparation of positive electrode.
According to stoichiometric proportion (1.05: 0.4: 0.2: 0.4) take analytically pure CH 3cOOLi, Ni (CH 3cOO) 2, Co (CH 3cOO) 2, Mn (CH 3cOO) 2with deionized water, fully dissolve respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix and with concentrated ammonia liquor, pH is adjusted to 7.5 left and right afterwards, 80 ℃ of heating water baths stir, and make the abundant complexing of various ions, and make moisture be evaporated to formation darkviolet gel; By gel under 120 ℃ of conditions dry 10 hours, and be placed at 500 ℃ preliminary treatment 6 hours, cooling rear grinding, then within 20 hours, obtain required product in 850 ℃ of roastings.
Embodiment 1
(1) preparation of gel: take analytically pure CH according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: 0.03) 3cOOLi, Ni (CH 3cOO) 2, Co (CH 3cOO) 2, Mn (CH 3cOO) 2, LiCl, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix and with concentrated ammonia liquor, pH value is adjusted to 7 left and right afterwards, at 60 ℃ of Water Unders, bathe heating and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel prepared by step (1) heat drying 8 hours at 80 ℃, by products therefrom pre-burning cooling grinding after 4 hours at 300 ℃, then calcine cooling grinding after 10 hours at 700 ℃, obtain product LiNi 0.4co 0.2mn 0.4o 1.97cl 0.03positive electrode.
Embodiment 2
(1) preparation of gel: take analytically pure LiNO according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: 0.05) 3, Ni (NO 3) 2, Co (NO 3) 2, Mn (NO 3) 2, LiCl, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix and with concentrated ammonia liquor, pH value is adjusted to 7.5 left and right afterwards, at 80 ℃ of Water Unders, bathe heating and constantly stir, until obtain darkviolet gel;
(2) calcination: calcination: get gel prepared by step (1) heat drying 10 hours at 100 ℃, by products therefrom pre-burning cooling grinding after 5 hours at 400 ℃, then calcine cooling grinding after 15 hours at 850 ℃, obtain product LiNi 0.4co 0.2mn 0.4o 1.95cl 0.05positive electrode.
Embodiment 3
(1) preparation of gel: take analytically pure LiOH, NiSO according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: 0.15) 4, CoSO 4, MnSO 4, LiCl, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix and all with concentrated ammonia liquor, pH value is adjusted to 8 left and right afterwards, at 90 ℃ of Water Unders, bathe heating and constantly stir, until obtain darkviolet gel;
(2) calcination: 2) calcination: get gel prepared by step (1) heat drying 12 hours at 120 ℃, by products therefrom pre-burning cooling grinding after 6 hours at 500 ℃, then calcine cooling grinding after 18 hours at 900 ℃, obtain product LiNi 0.4co 0.2mn 0.4o 1.85cl 0.15positive electrode.
Embodiment 4
(1) preparation of gel: take analytically pure CH according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: 0.05) 3cOOLi, Ni (CH 3cOO) 2, Co (NO 3) 2, Mn (NO 3) 2, LiF, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix and with concentrated ammonia liquor, pH value is adjusted to 7.5 left and right afterwards, at 100 ℃ of Water Unders, bathe heating and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel prepared by step (1) heat drying 15 hours at 150 ℃, by products therefrom pre-burning cooling grinding after 8 hours at 600 ℃, then calcine cooling grinding after 20 hours at 1000 ℃, obtain product LiNi 0.4co 0.2mn 0.4o 1.95f 0.05positive electrode.
Embodiment 5
(1) preparation of gel: take analytically pure LiNO according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: 0.1) 3, Ni (NO 3) 2, Co (NO 3) 2, Mn (NO 3) 2, LiF, complete with deionized water dissolving respectively, add citric acid solution, enter the mole sum that amount equals transition metal ions, mix and with concentrated ammonia liquor, pH value is adjusted to 7.5 left and right afterwards, at 90 ℃ of Water Unders, bathe heating and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel prepared by step (1) heat drying 14 hours at 100 ℃, by products therefrom pre-burning cooling grinding after 8 hours at 600 ℃, then calcine cooling grinding after 20 hours at 950 ℃, obtain product LiNi 0.4co 0.2mn 0.4o 1.9f 0.1positive electrode.
Embodiment 6
(1) preparation of gel: take analytically pure CH according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: 0.05) 3cOOLi, Ni (CH 3cOO) 2, Co (CH 3cOO) 2, Mn (CH 3cOO) 2, LiBr, complete with deionized water dissolving respectively, add citric acid solution, addition equals the mole sum of transition metal ions, mix and with concentrated ammonia liquor, pH value is adjusted to 7.5 left and right afterwards, at 80 ℃ of Water Unders, bathe heating and constantly stir, until obtain darkviolet gel;
(2) calcination: the gel of preparation heat drying 14 hours at 100 ℃, by products therefrom pre-burning cooling grinding after 6 hours at 600 ℃, then at 850 ℃, calcine cooling grinding after 18 hours, obtain product LiNi 0.4co 0.2mn 0.4o 1.95br 0.05positive electrode.
Known in the X-ray diffracting spectrum of comparative example and embodiment 2 from accompanying drawing 1, in embodiment 2, synthetic positive electrode has the hexagonal layer structure of high-sequential, does not occur belonging to the impurity peaks of doped chemical.
Known in the scanning electron microscope (SEM) photograph of embodiment 2 from accompanying drawing 2, at 850 ℃, the more tiny and particle diameter of synthetic embodiment 2 particles is evenly distributed, and smooth surface, and degree of crystallinity is better.
Application Example 1
By positive electrode powder synthetic in embodiment 1-6, acetylene black, poly-inclined to one side tetrafluoroethene (PVDF) is pressed mass fraction and was mixed than 80: 12: 8, after adding appropriate pyrrolidones, grind to form uniform sizing material, evenly coat on aluminium foil, at 100 ℃, dry, blunderbuss is cut (diameter 14mm), 3MPa rolls, make pole piece, through 80 ℃ of vacuumizes, after 12 hours, use, in the glove box that is full of argon gas, assemble button (CR2032) test battery, negative electricity is lithium sheet very, electrolyte is LB315[m (DMC): m (EMC): m (EC)=1: 1: 1] solution, barrier film is Celgard2325 hole film.The battery assembling is carried out to charge-discharge test with LAND-CT2001A.Discharging and recharging interval is 2-4.6V.
It should be noted that, specifically implement when of the present invention, because Li element in the positive electrode obtaining is volatile when the high-temperature calcination, have the Li loss of 5% left and right, so the actual mole dosage of lithium salts is wanted high 5% left and right compared with theoretical amount.
The battery that comparative example and the synthetic positive electrode of embodiment 1-6 are assembled into 0.2C current density under minute as shown in table 1 in the Electrochemical Characterization result of normal temperature and 55 ℃.During battery normal temperature that comparative example and the synthetic positive electrode of embodiment 1-6 are assembled into, under 1C current density, after 40 circulations, specific discharge capacity is as shown in table 2.
The battery that the positive electrode of comparative example and embodiment 1-3 is assembled, the cyclic curve figure when normal temperature under 0.2C electric current is as shown in Figure 3; The battery that the positive electrode of comparative example and embodiment 1-3 is assembled, the cyclic curve figure in the time of 55 ℃ under 0.2C electric current is as shown in Figure 4; The battery that the positive electrode of comparative example and embodiment 2,4,6 is assembled, the cyclic curve figure in the time of 55 ℃ under 0.2C electric current is as shown in Figure 5; The cyclic curve figure of the battery that the positive electrode of comparative example and embodiment 4 is assembled under different multiplying as shown in Figure 6.
Under table 10.2C current density, each embodiment charge-discharge performance test result is as shown in the table:
During table 2 normal temperature, the specific discharge capacity under 1C electric current after 40 circulations is as shown in the table:
Material Specific discharge capacity (mAh/g)
Comparative example 151.45
Embodiment 1 155.4
Embodiment 2 162.7
Embodiment 3 157.6
Embodiment 4 160.9
Embodiment 5 158.8
Embodiment 6 158.3

Claims (7)

1. the lithium ion battery of anion doped modification (4:4:2) type tertiary cathode material, is characterized in that: described positive electrode is LiNi 0.4co 0.2mn 0.4o 2-zx z, wherein X is F, Cl or Br, 0 < Z≤0.15.
According to mol ratio, take solubility lithium salts, nickel salt, manganese salt, cobalt salt, X salt, respectively with after deionized water dissolving, add citric acid solution mixing and stirring, with heating evaporation after concentrated ammonia liquor adjusting pH, obtain gel.After gel heat drying, after grinding, twice calcination obtain lithium ion battery (4:4:2) the type tertiary cathode material of the anion doped modification of product.
2. the lithium ion battery of anion doped modification (4:4:2) type tertiary cathode material, step is as follows:
(1) preparation of gel: according to stoichiometric proportion (1.05: 0.4: 0.2: 0.4: z) take analytically pure lithium salts, nickel salt, cobalt salt, manganese salt, X salt and be dissolved in respectively in deionized water, add citric acid solution, addition equals the mole sum of transition metal ions, mixing and stirring, with concentrated ammonia liquor, regulate pH value to 7-8,60-100 ℃ of heating water bath evaporation, and constantly stir, until obtain darkviolet gel;
(2) calcination: get gel dry 8-15 hour at 80-150 ℃ prepared by step (1), process 4-8 hour and be placed on 300-600 ℃ of pre-calcination; Naturally cool to grinding at room temperature and obtain presoma; Powder after grinding is placed in roasting 10-20 hour under 700-1000 ℃ of condition, and lithium ion battery (4:4:2) the type tertiary cathode material that obtains the anion doped modification of product is ground in cooling rear continuation.
3. the preparation method of the ternary cathode material of lithium ion battery of anion doped modification as claimed in claim 2, is characterized in that: described lithium salts is LiNO 3, CH 3one or more in COOLi, LiOH.
4. the preparation method of the ternary cathode material of lithium ion battery of anion doped modification as claimed in claim 2, is characterized in that: described nickel salt is Ni (NO 3) 2, Ni (CH 3cOO) 2, NiSO 4in one or more.
5. the preparation method of the ternary cathode material of lithium ion battery of anion doped modification as claimed in claim 2, is characterized in that: described manganese salt is Mn (NO 3) 2, Mn (CH 3cOO) 2, MnSO 4in one or more.
6. the preparation method of the ternary cathode material of lithium ion battery of anion doped modification as claimed in claim 2, is characterized in that: described cobalt salt is Co (NO 3) 2, Co (CH 3cOO) 2, CoSO 4in one or more.
7. the preparation method of the ternary cathode material of lithium ion battery of anion doped modification as claimed in claim 2, is characterized in that: described X salt is a kind of in LiCl, LiF, LiBr.
CN201310023488.5A 2013-01-23 2013-01-23 Anion doped modified lithium ion battery (4:4:2) type ternary cathode material and preparing method thereof Pending CN103943841A (en)

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CN105895903A (en) * 2014-12-25 2016-08-24 江南大学 Synthesis of modified lithium-rich layered positive electrode material doped with anions of F<->, Cl<-> and Br<->
CN106058238A (en) * 2016-07-25 2016-10-26 四川省有色冶金研究院有限公司 Modified spherical nickel cobalt lithium manganate NCM622 anode material and preparation method thereof
CN108807887A (en) * 2018-05-31 2018-11-13 电子科技大学 A kind of dual modified anode material for lithium-ion batteries of aluminium fluorine and preparation method thereof
CN109616658A (en) * 2018-12-17 2019-04-12 中科廊坊过程工程研究院 A kind of selenium, the nickelic positive electrode of sulfate radical codope and its preparation method and application
CN109659537A (en) * 2018-12-19 2019-04-19 上海纳米技术及应用国家工程研究中心有限公司 Citrate assists Fluorin doped ternary nano piece/polypyrrole preparation method and product and application
CN111463427A (en) * 2020-04-15 2020-07-28 江南大学 Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof

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CN105895903A (en) * 2014-12-25 2016-08-24 江南大学 Synthesis of modified lithium-rich layered positive electrode material doped with anions of F<->, Cl<-> and Br<->
CN105742627A (en) * 2016-04-15 2016-07-06 合肥工业大学 Preparation method for LiNi<x>Co<y>Mn<1-x-y>Br<z>O<2-z>/graphene composite cathode material
CN106058238A (en) * 2016-07-25 2016-10-26 四川省有色冶金研究院有限公司 Modified spherical nickel cobalt lithium manganate NCM622 anode material and preparation method thereof
CN108807887A (en) * 2018-05-31 2018-11-13 电子科技大学 A kind of dual modified anode material for lithium-ion batteries of aluminium fluorine and preparation method thereof
CN109616658A (en) * 2018-12-17 2019-04-12 中科廊坊过程工程研究院 A kind of selenium, the nickelic positive electrode of sulfate radical codope and its preparation method and application
CN109616658B (en) * 2018-12-17 2021-10-19 中科廊坊过程工程研究院 Selenium and sulfate radical co-doped high-nickel cathode material and preparation method and application thereof
CN109659537A (en) * 2018-12-19 2019-04-19 上海纳米技术及应用国家工程研究中心有限公司 Citrate assists Fluorin doped ternary nano piece/polypyrrole preparation method and product and application
CN111463427A (en) * 2020-04-15 2020-07-28 江南大学 Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof

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Application publication date: 20140723