CN100353594C - Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology - Google Patents
Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology Download PDFInfo
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- CN100353594C CN100353594C CNB2005100827706A CN200510082770A CN100353594C CN 100353594 C CN100353594 C CN 100353594C CN B2005100827706 A CNB2005100827706 A CN B2005100827706A CN 200510082770 A CN200510082770 A CN 200510082770A CN 100353594 C CN100353594 C CN 100353594C
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- 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 a method of preparing metal oxide electrode material which is provided with dopant. Active substances are directly deposited on a current collector basal body via electrodeposit and are soaked in binder of high polymer or high molecular polymer, and the electrode material of doped metal oxide is obtained after heat treatment preparation. The prepared electrode material of doped metal oxide is used as an anode, a pure lithium plate is used as a cathode, electrolyte is 1M LiPF6 /EC+DMC (1: 1), and a battery diaphragm is a millipore polypropylene diaphragm. Simulation battery assembly is carried out in a glove box which is filled with argon gas, and an LAND battery test system is used for constant current charge and discharge tests at room temperature. A primary lithium discharge capacity is 919mAh/g, and the lithium discharge capacity at the 50th circulation is 632mAh/g.
Description
Technical field
The present invention relates to a kind of metal oxide electrode material that adopts electro-deposition, dip-coating, heat-treating profiled technology on matrix, to prepare to be doped with binding agent and the method for preparation thereof.
Background technology
As electrode material, its preparation method has powder to be pressed into method, grout coating process, rheological phase reaction and predecessor thermal decomposition method etc. with the oxide of metal and hydroxide (as: nickel, cobalt, molybdenum etc.).Different manufacture methods respectively has its characteristics, and rheology phase chemistry method, to be pressed into method equipment simple, easy to operate, comparatively economical, and general battery string all can adopt; Grout coating process is used also more general, is used for secondary cell more.
Use electrodeposition process to prepare lithium ion battery negative material and start from 1994, begun to study by the J.Yang of Germany and the OSACA of Japan, mainly be confined to electro-deposition tin and kamash alloy material, the present specific capacity of Sn-Cu alloy that is obtained can reach 800mAh/g.Yet because the structure problem of kamash alloy own causes serondary lithium battery efflorescence to occur with the cycle-index increase, electrical property descends and causes losing efficacy.
Electro-deposition method, i.e. galvanization in plating bath, the charged particle that suspends in the plating bath are subjected to electric field influence and move and deposit on the matrix, thus the preparation sedimentary deposit.The size of the quality of sedimentary deposit and character and charged particle, size, the inertia degree, surperficial degree of charge and solution ontological property, electrical current waveform and density size etc. are relevant.
Summary of the invention
The objective of the invention is to propose a kind of metal oxide electrode material that contains alloy and preparation method thereof, be to adopt the electrodeposit metals hydroxide materials, after being soaked in binding agent again, and then heat-treating moulding, is directly active material to be deposited on the basis material.
A kind of preparation of the present invention contains the method for the metal oxide electrode material of alloy, comprises the following steps:
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte; Main salt component is Co (NO
3)
2Or Ni (NO
3)
2Or the acetate of the sulfate of the nitrate of iron, zinc or cobalt, nickel, iron, zinc or cobalt, nickel, iron, zinc, concentration is at 0.01～5mol;
Regulate electric depositing solution pH value 1～7 with nitric acid or sulfuric acid or acetic acid;
Second step: the oxide layer of removing matrix surface;
The 3rd step: beginning electrodeposit metals hydroxide materials in the electro-deposition aqueous solution that will prepare through the matrix immersion first step after second step handled;
The 4th step: will after the matrix after the 3rd step handled is put into deionized water to soak 1～5 hour, take out; Put into and take out after O.1～5 binder solution soaks hour, the volume ratio of binding agent and deionized water is 1: 10～500; Heat-treat at 50～500 ℃ then;
Described binding agent is a butadiene-styrene rubber;
The 5th step: will be through the matrix after the 4th step heat treatment, at 1～100MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix metal oxide materials that is doped with binding agent.
Described preparation contains the method for the metal oxide electrode material of alloy, and its matrix is meant nickel foil, aluminium foil, Copper Foil, graphite, nickel plate, platinized platinum, porous foam nickel, porous foam copper or porous foam aluminium.
Advantage of the present invention: adopt behind the electrodeposition technology and be soaked in the binding agent, heat-treat then, thisly directly active material is deposited on the preparation method that one-shot forming on the basis material prepares electrode, its technology is easy, and is with low cost.Scantling that this method obtains, shape, controllable microstructure, specific area is big.Material specific capacity that this method obtains, specific energy, specific power height, cycle performance are good.Be 450～919mAh/g to the maximum, the Co of doping butadiene-styrene rubber putting the lithium capacity first
30
4Electrode material reach about 632.5mAh/g the 50th circulation time specific capacity.
Description of drawings
Fig. 1 is put charge graph in first three week of embodiment 1.
Fig. 2 is specific capacity and the cycle-index curve chart of embodiment 1.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
The present invention is a kind of metal oxide electrode material that contains alloy of preparation, this electrode material prepares on matrix by adopting electro-deposition, dip-coating, heat-treating profiled technology, promptly adopt electrodeposit metals hydroxide, and it is soaked in the binding agent, heat-treat then and prepare the oxide electrode material that contains the doping binding agent.In the present invention, binding agent is immersed in the surface of sedimentary deposit metal oxide materials, has effectively reduced the change in volume that metal oxide materials produces in charge and discharge process.
The present invention prepares comprising the following steps: of a kind of metal oxide electrode material that contains alloy
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte, and main salt component is Co (NO
3)
2Or Ni (NO
3)
2Or the acetate of the sulfate of the nitrate of iron, zinc or cobalt, nickel, iron, zinc or cobalt, nickel, iron, zinc, concentration is at 0.01～5mol, with nitric acid or sulfuric acid regulation solution pH value 1～7.
Second step: the oxide layer of removing matrix surface;
Adopt conventional process for treating surface, as: polish, deoil, the activation of weak burn into.
The 3rd step: beginning electrodeposit metals hydroxide materials in the electro-deposition aqueous solution that will prepare through the matrix immersion first step after second step handled;
The 4th step: will after the matrix after the 3rd step handled is put into deionized water to soak 1～5 hour, take out; Put into binder solution again and soak taking-up after 1～5 hour, the ratio of binding agent and deionized water is 1: 10～500; Heat-treat at 50～500 ℃ then;
The 5th step: will be through the matrix after the 4th step heat treatment, at 1～100MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix metal oxide materials of doping binding agent.
With the matrix of the above-mentioned metal oxide materials that contains the doping binding agent for preparing positive pole as battery, be negative pole with the pour lithium slice, electrolyte is 1M LiPF
6/ EC+DMC (1: 1), battery diaphragm are microporous polypropylene membrane.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test.It is put the lithium capacity first and is 450～919mAh/g to the maximum.
Embodiment 1: deposition cobalt hydroxide electrode material on matrix
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte, and main salt component is Co (NO
3)
2, concentration is regulated electric depositing solution pH value 6～7 at 0.5mol with nitric acid.
Second step: the oxide layer of removing the copper matrix surface;
Adopt conventional process for treating surface, as: polish, deoil, the activation of weak burn into.
The 3rd step: beginning electro-deposition cobalt hydroxide material in the electro-deposition aqueous solution that will prepare through the copper matrix immersion first step after second step handled;
The 4th step: will put into through the matrix after the 3rd step handled and take out after deionized water soaks 3 hours; Put into SBR emulsion again and soak taking-up after 20 minutes, the volume ratio of SBR emulsion and deionized water is 1: 100; Carry out vacuum heat at 245 ℃ then;
The 5th step: will be through the matrix after the 4th step heat treatment, at 40MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix Co of doping butadiene-styrene rubber
3O
4Material.
With the above-mentioned Co that contains doping butadiene-styrene rubber for preparing
3O
4The matrix of material is negative pole as the positive pole of battery with the pour lithium slice, and electrolyte is 1M LiPF
6/ EC+DMC (1: 1), battery diaphragm are microporous polypropylene membrane.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test.It puts the lithium capacity first is 919mAh/g, and putting the lithium capacity to the 50 circulation time is 632mAh/g.
Embodiment 2: deposition zinc hydroxide electrode material on matrix
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte, and main salt component is Zn (NO
3)
2, concentration is regulated electric depositing solution pH value 6～7 at 0.5mol with nitric acid.
Second step: the oxide layer of removing the copper matrix surface;
Adopt conventional process for treating surface, as: polish, deoil, the activation of weak burn into.
The 3rd step: beginning electro-deposition zinc hydroxide material in the electro-deposition aqueous solution that will prepare through the copper matrix immersion first step after second step handled;
The 4th step: will put into through the matrix after the 3rd step handled and take out after deionized water soaks 1 hour; Put into SBR emulsion again and soak taking-up after 10 minutes, the volume ratio of SBR emulsion and deionized water is 1: 50; Carry out vacuum heat at 245 ℃ then;
The 5th step: will be through the matrix after the 4th step heat treatment, at 50MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix zinc oxide material of doping butadiene-styrene rubber.
With the matrix of the above-mentioned zinc oxide material that contains doping butadiene-styrene rubber for preparing positive pole as battery, be negative pole with the pour lithium slice, electrolyte is 1M LiPF
6/ EC+DMC (1: 1), battery diaphragm are microporous polypropylene membrane.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test.It puts the lithium capacity first is 710mAh/g, and putting the lithium capacity to the tenth circulation time is 232mAh/g.
Embodiment 3: deposition iron hydroxide electrode material on matrix
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte, and main salt component is Fe (NO
3)
2, concentration is regulated electric depositing solution pH value 6～7 at 0.5mol with nitric acid.
Second step: the oxide layer of removing the copper matrix surface;
Adopt conventional process for treating surface, as: polish, deoil, the activation of weak burn into.
The 3rd step: beginning electro-deposition iron hydroxide material in the electro-deposition aqueous solution that will prepare through the copper matrix immersion first step after second step handled;
The 4th step: will put into through the matrix after the 3rd step handled and take out after deionized water soaks 1 hour; Put into ptfe emulsion again and soak taking-up after 10 minutes, the volume ratio of ptfe emulsion and deionized water is 1: 100; Carry out vacuum heat at 245 ℃ then;
The 5th step: will be through the matrix after the 4th step heat treatment, at 40MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix iron oxide material of doping polytetrafluoroethylene.
With the matrix of the above-mentioned iron oxide material that contains the doping polytetrafluoroethylene for preparing positive pole as battery, be negative pole with the pour lithium slice, electrolyte is 1M LiPF
6/ EC+DMC (1: 1), battery diaphragm are microporous polypropylene membrane.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test.It puts the lithium capacity first is 530mAh/g, and putting the lithium capacity to the tenth circulation time is 150mAh/g.
Embodiment 4: deposition cobalt hydroxide electrode material on matrix
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte, and main salt component is Co (NO
3)
2, concentration is regulated electric depositing solution pH value 6～7 at 0.5mol with nitric acid.
Second step: choosing matrix is active carbon plate, and this matrix need not to carry out surface treatment.
The 3rd step: the active carbon sheet matrix is immersed beginning electro-deposition cobalt hydroxide material in the electro-deposition aqueous solution that the first step prepared;
The 4th step: will put into through the matrix after the 3rd step handled and take out after deionized water soaks 1 hour; Put into SBR emulsion again and soak taking-up after 20 minutes, the volume ratio of SBR emulsion and deionized water is 1: 250; Carry out vacuum heat at 245 ℃ then;
The 5th step: will be through the matrix after the 4th step heat treatment, at 20MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix Co of doping butadiene-styrene rubber
3O
4Material.
With the above-mentioned Co that contains doping butadiene-styrene rubber for preparing
3O
4The matrix of material is negative pole as the positive pole of battery with the pour lithium slice, and electrolyte is 1M LiPF
6/ EC+DMC (1: 1), battery diaphragm are microporous polypropylene membrane.In being full of the glove box of argon gas, carry out the assembling of simulated battery.Adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test.It puts the lithium capacity first is 450mAh/g, and putting the lithium capacity to the 50 circulation time is 370mAh/g.
Claims (4)
1, a kind of preparation contains the method for the metal oxide electrode material of alloy, includes the following step:
The first step: preparation electric depositing solution;
With the aqueous solution is electrolyte; Main salt component is Co (NO
3)
2Or Ni (NO
3)
2Or the acetate of the sulfate of the nitrate of iron, zinc or cobalt, nickel, iron, zinc or cobalt, nickel, iron, zinc, concentration is at 0.01～5mol;
Regulate electric depositing solution pH value 1～7 with nitric acid or sulfuric acid or acetic acid;
Second step: the oxide layer of removing matrix surface;
The 3rd step: beginning electrodeposit metals hydroxide materials in the electro-deposition aqueous solution that will prepare through the matrix immersion first step after second step handled;
It is characterized in that: also comprised for the 4th step: will after the matrix after the 3rd step handled is put into deionized water to soak 1～5 hour, take out; Put into binder solution again and soak taking-up after 0.1～5 hour, the volume ratio of binding agent and deionized water is 1: 10～500; Heat-treat at 50～500 ℃ then;
Described binding agent is a butadiene-styrene rubber;
The 5th step: will be through the matrix after the 4th step heat treatment, at 1～100MPa/cm
2The lower sheeting moulding promptly obtains depositing on the matrix metal oxide materials that is doped with binding agent.
2, preparation according to claim 1 contains the method for the metal oxide electrode material of alloy, it is characterized in that: described matrix is meant nickel foil, aluminium foil, Copper Foil, graphite, nickel plate, platinized platinum, porous foam nickel, porous foam copper or porous foam aluminium.
3, preparation according to claim 1 contains the method for the metal oxide electrode material of alloy, it is characterized in that: the electrode with the metal oxide of alloy is a positive pole, is negative pole with the pour lithium slice, and electrolyte is 1MLiPF
6/ EC+DMC, battery diaphragm are microporous polypropylene membrane, carry out the assembling of simulated battery in being full of the glove box of argon gas, adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test, and it is put the lithium capacity first and is 450～919mAh/g to the maximum.
4, preparation according to claim 1 contains the method for the metal oxide electrode material of alloy, it is characterized in that: the Co with doping butadiene-styrene rubber for preparing
3O
4Material is negative pole as positive pole with the pour lithium slice, and electrolyte is 1MLiPF
6/ EC+DMC, battery diaphragm is a microporous polypropylene membrane, in being full of the glove box of argon gas, carry out the assembling of simulated battery, adopt the LAND battery test system at room temperature to carry out the constant current charge-discharge test, it puts the lithium capacity first is 919mAh/g, and putting the lithium capacity to the 50 circulation time is 632mAh/g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100827706A CN100353594C (en) | 2005-07-12 | 2005-07-12 | Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology |
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|---|---|---|---|
| CNB2005100827706A CN100353594C (en) | 2005-07-12 | 2005-07-12 | Metal oxide electrode material for producing adulterant utilizing electro-deposition-heat treatment technology |
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| CN100353594C true CN100353594C (en) | 2007-12-05 |
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| CN101886330B (en) * | 2010-06-10 | 2012-07-11 | 天津大学 | Fe-Co magnetic alloy plated carbon fiber, preparation method and application thereof |
| CN102332570B (en) * | 2011-08-04 | 2013-10-30 | 佛山市邦普循环科技有限公司 | Method for manufacturing tin-stibium-nickel alloy cathode material of lithium ion battery |
| CN102677118B (en) * | 2012-05-03 | 2014-12-31 | 武汉威蒙环保科技有限公司 | Multipole type electro-deposition method for electrode of platy metal oxide |
| FR3002695B1 (en) * | 2013-02-28 | 2021-04-02 | I Ten | PROCESS FOR MANUFACTURING AN ENTIRELY SOLID MONOLITHIC BATTERY |
| CN104973661B (en) * | 2014-04-10 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of composite cathode electrode and its preparation method and application |
| CN104466202B (en) * | 2014-12-16 | 2016-11-30 | 北京化工大学常州先进材料研究院 | Prepared by the nickel oxide nano porous lithium O for cathode of air battery material of the supported active metals of a kind of Fluorin doped |
| CN105908493A (en) * | 2016-04-19 | 2016-08-31 | 郑州四维特种材料有限责任公司 | Metal modified carbon fiber, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1492080A (en) * | 2003-09-28 | 2004-04-28 | 北京航空航天大学 | Process for preparing nickel hydroxide material using electric deposition method |
| CN1540037A (en) * | 2003-10-31 | 2004-10-27 | 北京航空航天大学 | Method for preparing cobalt oxide by using electro deposition process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1492080A (en) * | 2003-09-28 | 2004-04-28 | 北京航空航天大学 | Process for preparing nickel hydroxide material using electric deposition method |
| CN1540037A (en) * | 2003-10-31 | 2004-10-27 | 北京航空航天大学 | Method for preparing cobalt oxide by using electro deposition process |
Non-Patent Citations (1)
| Title |
|---|
| 电沉积-烧结制备Co3O4锂离子电池负极及电性能 于维平等.材料热处理学报，第25卷第4期 2004 * |
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