CN1182607C - 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
CN1182607C
CN1182607C CNB031144780A CN03114478A CN1182607C CN 1182607 C CN1182607 C CN 1182607C CN B031144780 A CNB031144780 A CN B031144780A CN 03114478 A CN03114478 A CN 03114478A CN 1182607 C CN1182607 C CN 1182607C
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alloy material
cathode
plasma
cathode alloy
oxygen
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Chinese (zh)
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CN1431728A (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
    • H01M4/13—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
    • H01M4/04—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
    • H01M4/36—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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention discloses a technology for preparing anode materials of a lithium ion battery. Firstly, cathode alloy materials are formed by that Li, and transition metal elements M and Mn are carried out on proportion according to the chemistry general expression of Li-(1+x) M-<y>Mn-(2-x-y), the 'X' is bigger than or equal to-0.2 and is smaller than or equal to 0.2, and the 'y' is bigger than or equal to 0 and is smaller than or equal to 0.5; the voltages of 100v to 50kv exerts on the cathode alloy materials to make the cathode alloy materials into an ionization mode in a plasma reacting chamber in the temperature of 0 to 1000 DEG C under the oxygen partial pressure of 0.01 to 100 torr, wherein the electric current density of discharge is from 1 to 1000 mA/cm<2>, and the excitation frequency is from 0.5 to 35 MHz. The chemical general expression for the present invention to make the lithium ion battery cathode materials is Li-(1+x) M-yMn-(2-x-y) O-4. Because the present invention directly makes the alloying metals formed into the plasma adopting the vapor reaction method of the plasma which is reacted with oxygen then, the uniform mixing in atomic level is realized. Not only do reaction products have no hetero phases, the granularity of the products is small, and the dispersion type of particle diameter is also small.

Description

The preparation method of anode material for lithium-ion batteries
One, technical field
The present invention relates to a kind of preparation method of cell positive material, particularly a kind of preparation method of anode material for lithium-ion batteries.
Two, background technology
The preparation method of existing spinel-type lithium-ion cell positive material utilizes solid reaction process to make under high temperature more than 750 ℃ 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 spinelle crystalline structure, epigranular, grain type rule, average grain diameter less than 150 nanometers, the preparation method of the anode material for lithium-ion batteries of charge/discharge capacity height, good cycle.
For achieving the above object, the preparation method that the present invention adopts is: at first press chemical general formula Li (1+x)M yMn (2-x-y), carry out proportioning and make the cathode alloy material, wherein M is Co, Ni, Cr ,-0.2≤x≤0.2,0≤y≤0.5; In partial pressure of oxygen is 1.333-13300Pa, and temperature is that the target alloy material applies the voltage of 100V-50kV with the cathode alloy material plasmaization in 0-1000 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 1-1000mA/cm 2, stimulating frequency is 0.5-30MHz.
Because using plasma vapor reaction method of the present invention directly forms plasma with alloying metal, then with oxygen reaction, has realized the even mixing of atom level, not only product does not have dephasign, and the product granularity is little, and the particle size dispersion type is also little.
Four, embodiment
Embodiment 1, at first Li and Mn pressed chemical formula Li 1.2Mn 1.8Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 13300Pa, and temperature is that the target alloy material applies the voltage of 100V with the cathode alloy material plasmaization in 1000 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 700mA/cm 2, stimulating frequency is 0.5MHz, lithium ion battery anode is Li 1.2Mn 1.8O 4
Embodiment 2, at first Li, transition metal Co and Mn pressed chemical formula Li 1Co 0.5Mn 1.5Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 10664Pa, and temperature is that the target alloy material applies the voltage of 50kV with the cathode alloy material plasmaization in 0 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 700mA/cm 2, stimulating frequency is 20MHz, lithium ion battery anode is Li 1Co 0.5Mn 1.5O 4
Embodiment 3, at first Li, transition metal Cr and Mn pressed chemical formula Li 1.1Cr 0.1Mn 1.8Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 6665Pa, and temperature is that the target alloy material applies the voltage of 30kV with the cathode alloy material plasmaization in 800 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 500mA/cm 2, stimulating frequency is 15MHz, lithium ion battery anode is Li 1.1Cr 0.1Mn 1.8O 4
Embodiment 4, at first Li, transition metal Ni and Mn pressed chemical formula Li 0.9Ni 0.2Mn 1.9Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 2666Pa, and temperature is that the target alloy material applies the voltage of 10kV with the cathode alloy material plasmaization in 500 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 1mA/cm 2, stimulating frequency is 30MHz, lithium ion battery anode is Li 0.9Ni 0.2Mn 1.9O 4
Embodiment 5, at first Li, transition metal Co and Mn pressed chemical formula Li 0.8Co 0.4Mn 1.8Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 1333Pa, and temperature is that the target alloy material applies the voltage of 800V with the cathode alloy material plasmaization in 300 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 1000mA/cm 2, stimulating frequency is 1MHz, lithium ion battery anode is Li 0.8Co 0.4Mn 1.8O 4
Embodiment 6, at first Li, transition metal Cr and Mn pressed chemical general formula LiCr 0.3Mn 1.7Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 1.333Pa, and temperature is that the target alloy material applies the voltage of 300V with the cathode alloy material plasmaization in 600 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 400mA/cm 2, stimulating frequency is 0.5MHz, lithium ion battery anode is LiCr 0.3Mn 1.7O 4
The chemical general formula of the anode material for lithium-ion batteries that the present invention makes is Li (1+x)M yMn (2-x-y)(wherein M is one or more of transition metal,-0.2≤x≤0.2,0≤y≤0.5) has comparatively complete spinelle 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, the preparation method of anode material for lithium-ion batteries is characterized in that:
1) be that Co, Ni, Cr and Mn are by chemical general formula Li at first with Li, transition metal M (1+x)M yMn (2-x-y)Carry out proportioning and make the cathode alloy material ,-0.2≤x≤0.2,0≤y≤0.5;
2) be 1.333-13300Pa in partial pressure of oxygen, temperature is that the target alloy material applies the voltage of 100V-50kV with the cathode alloy material plasmaization in 0-1000 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 1-1000mA/cm 2, stimulating frequency is 0.5-30MHz.
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≤0.1,0≤y≤0.4.
3, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li and Mn are pressed chemical formula Li 1.2Mn 1.8Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 13300Pa, and temperature is that the target alloy material applies the voltage of 100V with the cathode alloy material plasmaization in 1000 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 700mA/cm 2, stimulating frequency is 0.5MHz.
4, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li, transition metal Co and Mn are pressed chemical formula Li 1Co 0.5Mn 1.5Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 10664Pa, and temperature is that the target alloy material applies the voltage of 50kV with the cathode alloy material plasmaization in 0 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 700mA/cm 2, stimulating frequency is 20MHz.
5, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li, transition metal Cr and Mn are pressed chemical formula Li 1.1Cr 0.1Mn 1.8Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 6665Pa, and temperature is that the target alloy material applies the voltage of 30kV with the cathode alloy material plasmaization in 800 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 500mA/cm 2, stimulating frequency is 15MHz.
6, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li, transition metal Ni and Mn are pressed chemical formula Li 0.9Ni 0.2Mn 1.9Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 2666Pa, and temperature is that the target alloy material applies the voltage of 10kV with the cathode alloy material plasmaization in 500 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 1mA/cm 2, stimulating frequency is 30MHz.
7, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li, transition metal Co and Mn are pressed chemical formula Li 0.8Co 0.4Mn 1.8Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 1333Pa, and temperature is that the target alloy material applies the voltage of 800V with the cathode alloy material plasmaization in 300 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 1000mA/cm 2, stimulating frequency is 1MHz.
8, the preparation method of anode material for lithium-ion batteries according to claim 1 is characterized in that: at first Li, transition metal Cr and Mn are pressed chemical general formula LiCr 0.3Mn 1.7Carry out proportioning and make the cathode alloy material; In partial pressure of oxygen is 1.333Pa, and temperature is that the target alloy material applies the voltage of 300V with the cathode alloy material plasmaization in 600 ℃ the plasma-reaction-chamber, and wherein discharge current density is: 400mA/cm 2, stimulating frequency is 0.5MHz.
CNB031144780A 2003-01-29 2003-01-29 Technology for preparing anode material of lithium ion battery Expired - Fee Related CN1182607C (en)

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JP2008181726A (en) * 2007-01-24 2008-08-07 Matsushita Electric Ind Co Ltd Non-aqueous electrolyte secondary battery and its manufacturing method
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

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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: Preparing method of anode material of lithium cobalt, nickel, manganese, oxygen lithium ion battery

Granted publication date: 20041229

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

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Assignee: Danyang Fala Electronics Co., Ltd.

Assignor: Xi'an Jiaotong University

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