CN1187850C - Technology for preparing anode material of lithium ion battery - Google Patents

Technology for preparing anode material of lithium ion battery Download PDF

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Publication number
CN1187850C
CN1187850C CNB031144772A CN03114477A CN1187850C CN 1187850 C CN1187850 C CN 1187850C CN B031144772 A CNB031144772 A CN B031144772A CN 03114477 A CN03114477 A CN 03114477A CN 1187850 C CN1187850 C CN 1187850C
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alloy material
plasma
reaction
cathode
oxygen
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Expired - Fee Related
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CNB031144772A
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Chinese (zh)
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CN1431727A (en
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徐友龙
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Xian Jiaotong University
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Xian Jiaotong 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
    • H01M4/52—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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • H01M4/50—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
    • 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
    • H01M2004/027—Negative 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

Abstract

The present invention discloses technology for preparing positive electrode material of a lithium ion battery. Firstly, Li and a transition metal element are compounded according to a chemical general formula of Li [(1+x)]M[(1-x)], and the mixture is used as alloy material of a negative electrode, wherein x is larger than or equal to-0.2 and is smaller than or equal to 0.2; secondly, 100V to 50kV of voltage is applied to the alloy material of a negative electrode in a plasma reaction chamber with temperature of 0 to 1000 DEG C and oxygen partial pressure of 0.01 to 100 Torr, and negative electrode alloy material, etc. is ionized; current density of discharge is from 1 to 1000 mA/cm<2>, excitation frequency is from 0.5 to 35 MHz, the positive electrode material of a lithium ion battery is prepared, and the chemical general formula is Li [(1+x)]M[(1-x)]O2. In the present invention, because alloy metal forms plasma directly by a plasma vapor reaction method, and then the plasma and oxygen react, and uniform mixing of atom grades is realized; reaction products have no impurity phase, and the products have little particle sizes and little particle diameter dispersing types.

Description

A kind of preparation technology of anode material for lithium-ion batteries
One, technical field
The present invention relates to a kind of preparation technology of cell positive material, particularly a kind of preparation technology of anode material for lithium-ion batteries.
Two, background technology
The preparation technology of existing stratiform structure lithium ion battery positive electrode utilizes solid reaction process to make under high temperature more than 800 ℃ with containing after the oxide of lithium metal, manganese, cobalt, nickel etc. or hydroxide or salt adopt direct powder stock mechanical mixture again, when solid phase reaction, owing to be subjected to the influence of reactant granularity, the atom of reactant thoroughly evenly can't be mixed, cause more or less existing in the product impure dephasign product.In addition, because temperature is higher during solid phase reaction, the time is longer, and the granularity that causes product is big (several microns) all, and the granularity dispersiveness is also bigger.These factors not only cause the material charge/discharge capacity of solid phase reaction preparation on the low side, and cycle performance also is affected.
Three, summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned existing technology, provide a kind of preparation technology simple, have complete stratiform crystalline structure, epigranular, grain type rule, average grain diameter less than 150 nanometers, the preparation technology of the anode material for lithium-ion batteries of charge/discharge capacity height, good cycle.
For achieving the above object, the preparation technology that the present invention adopts is: at first Li and transition metal M are pressed chemical general formula Li (1+x)M (1-x)Carry out proportioning, as the cathode alloy material, wherein-0.2≤x≤0.2; At 0-1000 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 0.01-100Torr, and the target alloy material applies the voltage of 100V-50kV with the cathode alloy material plasmaization, and wherein discharge current density is: 1-1000mA/cm 2, stimulating frequency is 0.5-35MHz.
Because using plasma vapor reaction method of the present invention directly forms plasma with alloying metal, then with oxygen reaction, realized the even mixing of atom level, and product there is not dephasign, the product granularity is little, and the particle size dispersion type is little.
Four, embodiment
Embodiment 1, at first Li and transition metal Co pressed chemical formula Li 0.8Co 1.2Carry out proportioning as the cathode alloy material; At 1000 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 70Torr, and the target alloy material applies the voltage of 40kV with the cathode alloy material plasmaization, and wherein discharge current density is: 1000mA/cm 2, stimulating frequency is 28MHz, lithium ion battery anode is Li 0.8Co 1.2O 2
Embodiment 2, at first Li and transition metal Ni pressed chemical formula Li 1.2Ni 0.8Carry out proportioning as the cathode alloy material; At 700 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 90Torr, and the target alloy material applies the voltage of 50kV with the cathode alloy material plasmaization, and wherein discharge current density is: 1mA/cm 2, stimulating frequency is 35MHz, lithium ion battery anode is Li 1.2Ni 0.8O 2
Embodiment 3, at first Li and transition metal Mn pressed chemical formula Li 1.1Mn 0.9Carry out proportioning as the cathode alloy material; At 0 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 100Torr, and the target alloy material applies the voltage of 1kV with the cathode alloy material plasmaization, and wherein discharge current density is: 800mA/cm 2, stimulating frequency is 0.5MHz, lithium ion battery anode is Li 1.1Mn 0.9O 2
Embodiment 4, at first Li and transition metal Ni carried out proportioning as the cathode alloy material by chemical formula LiNi; At 400 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 0.01Torr, and the target alloy material applies the voltage of 13kV with the cathode alloy material plasmaization, and wherein discharge current density is: 200mA/cm 2, stimulating frequency is 10MHz, lithium ion battery anode is LiNiO 2
Embodiment 5, at first Li and transition metal Co pressed chemical formula Li 1.2Co 0.8Carry out proportioning as the cathode alloy material; At 100 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 10Torr, and the target alloy material applies the voltage of 500V with the cathode alloy material plasmaization, and wherein discharge current density is: 500mA/cm 2, stimulating frequency is 3MHz, lithium ion battery anode is Li 1.2Co 0.8O 2
Embodiment 6, at first Li and transition metal Mn pressed chemical formula Li 0.9Mn 1.1Carry out proportioning as the cathode alloy material; At 300 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 30Torr, and the target alloy material applies the voltage of 100V with the cathode alloy material plasmaization, and wherein discharge current density is: 300mA/cm 2, stimulating frequency is 17MHz, lithium ion battery anode is Li 0.9Mn 1.1O 2
The chemical general formula of the anode material for lithium-ion batteries that the present invention makes is: Li (1+x)M (1-x)O 2(wherein M is Co, Ni, Mn-0.2≤x≤0.2), have complete stratiform crystalline structure, epigranular, grain type rule, average grain diameter less than 150 nanometers, charge/discharge capacity is higher more than 20% than the same material of existing solid phase method preparation, and capacity loop attenuation rate reduces more than 10%.

Claims (8)

1, a kind of preparation method of anode material for lithium-ion batteries is characterized in that:
1) at first Li and transition metal M are pressed chemical general formula Li (1+x)M (1-x)Carry out proportioning, as the cathode alloy material, wherein M is Co, Ni, Mn ,-0.2≤x≤0.2;
2) be in the plasma-reaction-chamber of 0.01-100Torr at 0-1000 ℃, partial pressure of oxygen, the target alloy material applies the voltage of 100V-50kV with the cathode alloy material plasmaization, and wherein discharge current density is: 1-1000mA/cm 2, stimulating frequency is 0.5-35MHz.
2, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: in the proportioning of said cathode alloy material-and 0.1≤x≤0.1.
3, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and transition metal Co are pressed chemical formula Li 0.8Co 1.2Carry out proportioning as the cathode alloy material; At 1000 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 70Torr, and the target alloy material applies the voltage of 40kV with the cathode alloy material plasmaization, and wherein discharge current density is: 1000mA/cm 2, stimulating frequency is 28MHz.
4, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and transition metal Ni are pressed chemical formula Li 1.2Ni 0.8Carry out proportioning as the cathode alloy material; At 700 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 90Torr, and the target alloy material applies the voltage of 50kV with the cathode alloy material plasmaization, and wherein discharge current density is: 1mA/cm 2, stimulating frequency is 35MHz.
5, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and transition metal Mn are pressed chemical formula Li 1.1Mn 0.9Carry out proportioning as the cathode alloy material; At 0 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 100Torr, and the target alloy material applies the voltage of 1kV with the cathode alloy material plasmaization, and wherein discharge current density is: 800mA/cm 2, stimulating frequency is 0.5MHz.
6, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and transition metal Ni are carried out proportioning as the cathode alloy material by chemical formula LiNi; At 400 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 0.01Torr, and the target alloy material applies the voltage of 13kV with the cathode alloy material plasmaization, and wherein discharge current density is: 200mA/cm 2, stimulating frequency is 10MHz.
7, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and transition metal Co are pressed chemical formula Li 1.2Co 0.8Carry out proportioning as the cathode alloy material; At 100 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 10Torr, and the target alloy material applies the voltage of 500V with the cathode alloy material plasmaization, and wherein discharge current density is: 500mA/cm 2, stimulating frequency is 3MHz
8, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and transition metal Mn are pressed chemical formula Li 0.9Mn 1.1Carry out proportioning as the cathode alloy material; At 300 ℃, partial pressure of oxygen is in the plasma-reaction-chamber of 30Torr, and the target alloy material applies the voltage of 100V with the cathode alloy material plasmaization, and wherein discharge current density is: 300mA/cm 2, stimulating frequency is 17MHz.
CNB031144772A 2003-01-29 2003-01-29 Technology for preparing anode material of lithium ion battery Expired - Fee Related CN1187850C (en)

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CN101237041B (en) * 2008-01-29 2011-04-06 四川大学 Method for making lithium-included pole material with inter-metal compound of multi-element metal
CN109019703B (en) * 2017-05-25 2020-11-06 宁波工程学院 Plasma enhanced oxidation roasting method for high-nickel cathode material of lithium ion battery

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Assignee: Danyang Fala Electronics Co., Ltd.

Assignor: Xi'an Jiaotong University

Contract fulfillment period: 2006.10.12 to 2021.10.11 contract change

Contract record no.: 2008320000230

Denomination of invention: Process for preparing lithium ion cell positive pole material

Granted publication date: 20050202

License type: Exclusive license

Record date: 2008.9.22

LIC Patent licence contract for exploitation submitted for record

Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2006.10.12 TO 2021.10.11

Name of requester: DANYANG FALA ELECTRON CO., LTD.

Effective date: 20080922

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Assignee: Danyang Fala Electronics Co., Ltd.

Assignor: Xi'an Jiaotong University

Contract record no.: 2008320000230

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CF01 Termination of patent right due to non-payment of annual fee