CN1508894A - Positive electrode material for lithium ion cell and synthesizing method thereof - Google Patents

Positive electrode material for lithium ion cell and synthesizing method thereof Download PDF

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CN1508894A
CN1508894A CNA02128041XA CN02128041A CN1508894A CN 1508894 A CN1508894 A CN 1508894A CN A02128041X A CNA02128041X A CN A02128041XA CN 02128041 A CN02128041 A CN 02128041A CN 1508894 A CN1508894 A CN 1508894A
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lithium
compound
cooling
synthetic method
positive electrode
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CN1265483C (en
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于作龙
袁荣忠
瞿美臻
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Chengdu Institute of Organic Chemistry of CAS
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Chengdu Institute of Organic Chemistry of CAS
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

In the invention, chemical general expression of positive pole material is: LixNi0.8-y Co0.2MyOp, where M is Cd or Zn, X=0.97-1.2, Y=0-0.1, p=2-2(1+y). The material is synthesized through following steps: (1) grinding, mixing compound of lithium, compound of cobalt, and compound of nickel containing a small quantity of cadmium or zinc, or containing none cadmium and zinc in certain scale evenly; (2) preroasting mixed powers makes it crystallize partially; (3) careful grinding preroasted mixture evenly, then roasting is carried out right along under higher temperature, and obtaining the invented material of positive pole after cooling. The invention possesses advantages of high specific capacity of the material, good performances of charging and discharging cycle, even size of granule, and narrow distribution range as well as simple preparation technique.

Description

The positive electrode of lithium ion battery and synthetic method thereof
Technical field
The present invention relates to a kind of lithium ion battery, particularly a kind of positive electrode of lithium ion battery and synthetic method thereof.
Background technology
LiNiO 2Have and LiCoO 2Same structure: class α-NaFeO2 structure belongs to the R-3m space group, and close theoretical capacity 275mAh/g is arranged.LiNiO 2Because advantages such as capacity height, power are big, moderate cost became LiCoO in recent years again 2The focus that replaces investigation of materials, but also have synthetic difficult, problems such as the circulation volume decay is fast, poor heat stability, practicalization is slower always.Adopt the whole bag of tricks to improve LiNiO now 2Combination property, wherein at LiNiO 2In mix the solid solution LiNi that forms behind the Co element 1-yCo yO 2Be subjected to most numerous researchers' concern.Solid solution LiNi 1-yCo yO 2The advantage that has had both cobalt system and nickel based material, synthesis condition cost relatively gentleer, material is lower, and chemical property and cyclical stability are good simultaneously, show more excellent comprehensive performance, and its research is also reached its maturity, and are to be hopeful to substitute LiCoO most 2One of positive electrode, the especially more excellent LiNi of performance and price 0.8Co 0.2O 2Material, however to realize commercialization and practicability, still need do further effort aspect large-scale production, the stable performance.
Improving LiNi 0.8Co 0.2O 2The stable aspect of material, the multiple element that mixes can obtain reasonable effect, studies morely at present, as Mg, Ga, Sr, Al, Fe, Mn, Ti, F etc., has obtained certain progress.And admixture Cd or Zn element are to improving LiNi 0.8Co 0.2O 2Charge and discharge cycles stability is relative with Research on Thermal Stability less.In existing patent EP944.125, Takuya S.etal has reported that a spot of Cd of admixture or Zn element can improve LiNi 1-yCo yO 2Charge and discharge cycles stability, but do not do concrete deep research.Subramanian V. and Ting-Kuo Fey George[SolidState Ionics, Vol.148,351～358,2002] mix by high temperature solid state reaction roasting compressing tablet under the condition of 800 ℃ and logical Oxygen Flow
Thing got positive electrode LiNi in 20 hours 0.7Co 0.2Ti 0.05M 0.05O 2(M=Mg, Al or Zn), though cyclicity and thermal stability have greatly improved, capacity is on the low side, charging capacity the highest when M is Zn only reaches 120mAh/g.Remain further to be studied to improve synthetic method, prepare the better compound of combination property.
High-temperature solid phase reaction method has plurality of advantages such as preparation technology is simple, mechanization degree is high, the product crystal formation is good, is the prefered method that suitability for industrialized production is used, and also is synthetic LiNi 0.8Co 0.2O 2The method commonly used of material.Tsutomu Ohzuku et al [Electrochimica Acta., Vol.38,9,1993] adopts Li 2CO 3, CoCO 3And NiCO 3Raw material prepares LiNi through compressing tablet 1-yCo yO 2Composite oxides, but capacity is not more than 150mAh/g.W.Li et al [J.Electrochem.Soc., Vol.144,2773～2779,1997] adopts LiOHH 2O, Ni (OH) 2, Co 2O 3Synthetic for the logical oxygen calcining of raw material, make chemical property LiNi preferably 0.8Co 0.2O 2Material, but in preparation process for promoting the growth of crystal grain, added flux, want flush away flux catabolite at last, be unfavorable for commercial Application.With LiNiO 2The same, rich nickel LiNi 0.8Co 0.2O 2The material preparation process parameter is very big to the performance impact of material, not only be subjected to the influence of material choice, and be subjected to the control of synthesis condition, crystal structure, capacity and the cycle performance of different reaction raw materials resulting product behind different heat treatment approach all are very different, can be by optimizing the chemical property that synthesis condition improves this material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of higher charge ratio capacity and the better anode material for lithium-ion batteries of electrochemical stability and process of convenient and simple synthetic this positive electrode of keeping.
The technical scheme of technical solution problem of the present invention is: a kind of positive electrode of lithium ion battery, its chemical general formula is: Li xNi 0.8-yCo 0.2M yO pWherein M is Cd or Zn, x=0.97～1.2, y=0～0.1, p=2～2 (1+y).
The method of the positive electrode of the lithium ion battery that the present invention is synthetic above-mentioned is:
(a) with the compound of the compound of the lithium of certain proportion amount, cobalt and contain a small amount of cadmium or zinc or the raw materials of compound that do not contain the nickel of cadmium or zinc element grinds, ball milling mixes the formation mixed-powder;
(b) with mixed-powder preroast 6～10 hours under 550 ℃～650 ℃ temperature and air ambient earlier, take out cooling and also grind;
(c) mixed-powder after will cooling off and grind continues about 12～24 hours of roasting again under 700 ℃～800 ℃ the temperature and the condition of logical Oxygen Flow, is cooled to room temperature.
The invention has the beneficial effects as follows: a kind of anode material for lithium-ion batteries Li is provided xNi 0.8-yCo 0.2M yO p, the electrochemical stability of this material has greatly improved, and has simultaneously than higher charging and discharging capacity.Positive electrode Li of the present invention xNi 0.8-yCo 0.2M yO pAdopt improved solid phase substep preparation technology to make, optimized preparation process condition, raw material conveniently is easy to get, and without auxiliary processes such as granulation or compressing tablets, has simplified technology, has improved production efficiency, is easy to promote the realization industrial-scale production.The positive electrode crystal structure of method of the present invention preparation is complete, and it is also narrower that degree of crystallinity height, material powder granule particle diameter can be controlled in the distribution of positive pole powder particle size range granularity of submicron order.
Description of drawings
Fig. 1 is the material LiNi that is synthesized 0.8Co 0.2O 2The X-ray diffraction spectrogram.
Fig. 2 is the material LiNi that is synthesized 0.8Co 0.2O 2Scanning electron microscope diagram.
Fig. 3 is the material LiNi that is synthesized 0.8Co 0.2O 2Charging and discharging capacity--cycle-index graph of a relation.
Fig. 4 is the material Li that is synthesized 1.06Ni 0.74Co 0.19Cd 0.02O 2.04Scanning electron microscope diagram.
Fig. 5 is the material Li that is synthesized 1.06Ni 0.74Co 0.19Cd 0.02O 2.04The X-ray diffraction spectrogram.
Fig. 6 is the material Li that is synthesized 1.06Ni 0.74Co 0.19Cd 0.02O 2.04Specific discharge capacity-cycle-index graph of a relation.
Fig. 7 is the material Li that is synthesized 1.12Ni 0.75Co 0.2Zn 0.05O 2.07Specific discharge capacity-cycle-index graph of a relation.
Embodiment
The invention will be further described below in conjunction with accompanying drawing.
Earlier with the compound of the compound of a certain amount of lithium, cobalt and contain a small amount of cadmium or zinc or the raw materials of compound mixed grinding, the ball milling that do not contain the nickel of cadmium or zinc element evenly form mixed-powder.The compound of described lithium is hydronium(ion) oxidation lithium (LiOHH 2O), lithia (Li 2O), lithium acetate [Li (CH 3Or lithium carbonate (Li COO)] 2CO 3) in a kind of and lithium nitrate (LiNO 3) by 1: the formed mixture of the mixed of (0.5～1), the mixture granularity is in the scope of 5～50 μ m.The compound of described cobalt is the mixture of one or more compounds in the oxide, hydroxide, acetate, nitrate, carbonate, oxalates compound of cobalt, and its granularity is 0.1～100 μ m.The raw materials of compound of described nickel is used for the ball-shape nickel hydroxide [Ni (OH) of the electrode material of NI-G, nickel-hydrogen secondary cell for widespread commercialization 2] or add the ball-shape nickel hydroxide [Ni (OH) of Cd or Zn element and bag Co 2], granularity is 5～25 μ m.
When the preparation positive electrode active materials, be very necessary at first to fully mixing of raw material.It can be widely used various process for dispersing that the used mixing of the present invention disperses, as the grinding of dry powder solid phase mixing, ball milling, or be that the wet-mixed of dispersant is ground, ball milling with water, organic solvent (ethanol, acetone etc.), generally grind, the ball milling time is 1～24 hour.Also can adopt newer spray drying process to carry out, the time of the mixture after this method is disperseed during in heat treatment can be short, and temperature also can be hanged down.
The sintering temperature that the present invention prepares positive electrode active materials is 550～800 ℃.Adopt the substep method of roasting, the mixture that above-mentioned mixing is scattered roasting under 550～650 ℃ of temperature air environment, temperature retention time is 6～10 hours, is preferably 7～9 hours.Cooling rate after prebake burns down has bigger influence to the performance of material and the size of final particle, and general cooling rate is controlled to be greater than 5 ℃/minute, directly takes out the outer cooling of stove better.Mixture after process preroast is handled has partially crystallizable, and the while also makes the raw material that originally mixed produce new non-uniform areas owing to the fusing of lithium salts, and grinding, ball milling make it even so need once more.Continue roasting 12～24 hours again under the condition of 700～800 ℃ temperature and logical Oxygen Flow through the mixed powder after the preroast, 750 ℃ of left and right sides roastings 15～20 hours better, Oxygen Flow is controlled at 10～200ml/min.Cooling after roasting is intact is adopted with stove cooling or program control cooling, and logical oxygen protection continues to be cooled to room temperature then and takes out to below 450 ℃, promptly obtains material requested.
In the following embodiments, the material that obtains of the inventive method characterizes or tests with following method: the crystal structure of material adopts X-ray diffraction method to measure; Surface topography and granular size adopt scanning electron microscopy to measure; The chemical analysis of material is analyzed by carrying out ICP-AES; Chemical property detects the method for all knowing with the those of ordinary skill under this area, it is assembled into the button test cell tests, promptly use positive electrode active materials 85% of the present invention, acetylene black 10%, polyfluortetraethylene of binding element (PTFE) 5%, mixing the furnishing pulpous state is coated on the aluminium foil, dry back is as positive electrode in the vacuum drying chamber, with metal lithium sheet is to electrode, and U.S. Celgard 2400 is a barrier film, with 1M LiClO 4/ EC+DMC (1: 1) is an electrolyte, is assembled into test battery in being full of the stainless steel glove box of argon gas, and charge-discharge velocity is 0.2～0.5C, and discharging and recharging cut-ff voltage is 4.25～2.7V, carries out charge-discharge test with DC-5 type full-automatic battery controlled testing instrument.
Embodiment 1:
Synthetic positive electrode LiNi 0.8Co 0.2O 2
LiOHH with 0.58mol 2The LiNO of O (AR) and 0.5mol 3(AR) insert careful the grinding carefully in the agate mortar, other is with the Ni (OH) of 0.8mol 2The Co of (containing Ni is 61.35%) and 0.2mol 2O 3(CA) in agate mortar, grind evenly, two mixtures are mixed to grind evenly to form then and mix powder.Powder roasting 7 hours under 630 ℃ air ambient will be mixed, taking-up is cooled to room temperature, after the mixture of sintering ground to form the powder particle, heating rate with 250 ℃/hour in melting down again rises to 750 ℃ of left and right sides roastings 15 hours, logical simultaneously oxygen, oxygen gas flow rate keeps the stable 25ml/min that is controlled at, and roasting finishes the back and naturally cools to stove and stop logical oxygen below 450 ℃, continues to be chilled to take out after the room temperature and grinds.Analysis and characterization and Electrochemical results are shown in Fig. 1,2 and 3.Table-1 has been listed relevant test data, wherein I simultaneously 003/ I 104Be the intensity rate of (003) peak in the XRD test result with (104) peak, its the big more explanation crystallization degree of value and the degree of order are high more, the initial discharge specific capacity is a highest specific volume value in preceding 4 circulations, and capability retention is the 30th time the capacity and the ratio of initial discharge specific capacity, the coulombic efficiency of first charge-discharge efficiency for discharging and recharging for the first time.Below data implication among other embodiment identical therewith.
Table-1:
I 003/ I 104: 1.63 initial discharge specific capacity: 181.2mAh/g
Particle diameter: 200～1000nm is coulombic efficiency first: 85%
Capability retention: 83%
Embodiment 2:
The synthetic lithium-nickel-cobalt-oxygen thing positive electrode Li that contains cadmium xNi 0.8-yCo 0.2Cd yO p
With the spherical Ni (OH) that contains Cd 2(contain Ni and be 59.45%, Cd be 3.15%) replaces the Ni (OH) among the embodiment 1 2, other process conditions are consistent with embodiment 1.The chemical analysis of synthetic material is analyzed by carrying out ICP-AES, and the actual metered formula that records material is: Li 1.06Ni 0.74Co 0.19Cd 0.02O 2.04Other analysis and characterization and Electrochemical results have been listed relevant data simultaneously in table-2 shown in Fig. 4,5 and 6.
Table-2:
I 003/ I 104: 1.40 initial discharge specific capacity: 157.8mAh/g
Particle diameter: 200～700nm is coulombic efficiency first: 87.1%
Capability retention: 91%
Embodiment 3:
The synthetic lithium/nickel/cobalt composite oxide positive electrode LixNi that contains zinc 0.8-yCo 0.2Zn yO p
LiOHH with 0.65mol 2The LiNO of O (AR) and 0.5mol 3(AR) insert careful the grinding carefully in the agate mortar.The Ni (OH) that in addition high density of 0.8mol is contained Zn 2The Co of (contain Ni and be 60.03%, Zn be 4.14%) and 0.2mol 2O 3(CA) ball milling mixed it in 3 hours in planetary ball mill.Then two mixtures are mixed and grind evenly.The roasting 6 hours under 650 ℃ temperature and air ambient earlier of uniform mixture will be ground, taking-up is cooled to room temperature, after the mixture of sintering ground to form the powder particle, heating rate with 250 ℃/hour in melting down again rises to 750 ℃ of left and right sides roastings 16 hours, logical simultaneously oxygen, oxygen gas flow rate keeps the stable 15ml/min that is controlled at.After roasting finishes, adopt program control to reduce to and stop logical oxygen below 500 ℃, take out grinding after continuing to be chilled to room temperature.The chemical analysis of synthetic material is analyzed by carrying out ICP-AES, and the actual metered formula that records material is: Li 1.12Ni 0.75Co 0.2Zn 0.05O 2.07Data that other analysis and characterization and Electrochemical results are listed in-2 as table and capacity curve shown in Figure 3.
Table-3:
I 003/ I 104: 1.43 initial discharge specific capacity: 154.9mAh/g
Particle diameter: 100～800nm is coulombic efficiency first: 88.3%
Capability retention: 91.5%

Claims (8)

1. the positive electrode of a lithium ion battery, it is characterized in that: the chemical general formula of described positive electrode is: Li xNi 0.8-yCo 0.2M yO pWherein M is Cd or Zn, x=0.97～1.2, y=0～0.1, p=2～2 (1+y).
2. the synthetic method of the positive electrode of the described lithium ion battery of claim 1 is characterized in that: said method comprising the steps of:
(a) with the compound of the compound of the lithium of certain proportion amount, cobalt and contain a small amount of cadmium or zinc or the raw materials of compound that do not contain the nickel of cadmium or zinc element grinds, ball milling mixes;
(b) with mixed-powder preroast 6～10 hours under 550 ℃～650 ℃ temperature and air compression ring border in advance, take out cooling and also grind;
(c) mixed-powder after will cooling off and grind continues about 12～24 hours of roasting, follow procedure cooling again under 700 ℃～800 ℃ the temperature and the condition of logical Oxygen Flow.
3. the synthetic method of anode material for lithium-ion batteries according to claim 2, it is characterized in that: the compound of described lithium is LiOHH 2O, Li 2O, Li (CH 3COO) or Li 2CO 3In a kind of and LiNO 3By 1: the mixture of the mixed of (0.5～1), granularity are 5～50 μ m.
4. the synthetic method of anode material for lithium-ion batteries according to claim 2, it is characterized in that: the compound of described cobalt is the mixture of one or more compounds in the oxide of cobalt, hydroxide, acetate, nitrate, carbonate, the oxalates compound, and its granularity is 0.1～100 μ m.
5. the synthetic method of anode material for lithium-ion batteries according to claim 2, it is characterized in that: the raw materials of compound of described nickel is the spherical Ni (OH) that is used for the electrode material of NI-G, nickel-hydrogen secondary cell 2Or add the spherical Ni (OH) of Cd or Zn element and bag Co 2, granularity is 5～25 μ m.
6. the synthetic method of anode material for lithium-ion batteries according to claim 2 is characterized in that: outer cooling of stove or program control cooling are adopted in the cooling after the described mixed-powder preroast, and speed is greater than 5 ℃/minute.
7. the synthetic method of anode material for lithium-ion batteries according to claim 2, it is characterized in that: described Oxygen Flow is controlled at 10～200ml/min.
8. the synthetic method of anode material for lithium-ion batteries according to claim 2 is characterized in that: described follow procedure cooling for stove cooling or program control cooling and the protection of logical oxygen to below 450 ℃, continue to be cooled to room temperature then.
CNB02128041XA 2002-12-16 2002-12-16 Positive electrode material for lithium ion cell and synthesizing method thereof Expired - Fee Related CN1265483C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1300872C (en) * 2005-05-13 2007-02-14 北京化工大学 Columnar structure LiCoO2 electrode material and its preparing process
CN1319865C (en) * 2006-02-24 2007-06-06 长沙矿冶研究院 LiCoO for preparing lithium ion battery anode material2Method (2)
CN102754252A (en) * 2011-01-21 2012-10-24 Jx日矿日石金属株式会社 Method for producing positive-electrode active material for lithium-ion battery and positive-electrode active material for lithium-ion battery
EP2533334A4 (en) * 2010-02-05 2016-10-19 Jx Nippon Mining & Metals Corp Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery
CN106450283A (en) * 2016-11-23 2017-02-22 昆明理工大学 Preparing method of lithium-rich ternary anode material with high power capacity
CN104600287B (en) * 2014-12-25 2017-11-24 华中科技大学 A kind of preparation method and product of lithium nickel cobalt zinc-oxygen battery positive electrode

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1300872C (en) * 2005-05-13 2007-02-14 北京化工大学 Columnar structure LiCoO2 electrode material and its preparing process
CN1319865C (en) * 2006-02-24 2007-06-06 长沙矿冶研究院 LiCoO for preparing lithium ion battery anode material2Method (2)
EP2533334A4 (en) * 2010-02-05 2016-10-19 Jx Nippon Mining & Metals Corp Positive electrode active material for lithium ion battery, positive electrode for lithium ion battery, and lithium ion battery
CN102754252A (en) * 2011-01-21 2012-10-24 Jx日矿日石金属株式会社 Method for producing positive-electrode active material for lithium-ion battery and positive-electrode active material for lithium-ion battery
CN102754252B (en) * 2011-01-21 2014-12-17 Jx日矿日石金属株式会社 Method for producing positive-electrode active material for lithium-ion battery and positive-electrode active material for lithium-ion battery
CN104600287B (en) * 2014-12-25 2017-11-24 华中科技大学 A kind of preparation method and product of lithium nickel cobalt zinc-oxygen battery positive electrode
CN106450283A (en) * 2016-11-23 2017-02-22 昆明理工大学 Preparing method of lithium-rich ternary anode material with high power capacity

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