CN102104170A - Great-capacity high-power lithium secondary battery and preparation method thereof - Google Patents
Great-capacity high-power lithium secondary battery and preparation method thereof Download PDFInfo
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- CN102104170A CN102104170A CN2010106142192A CN201010614219A CN102104170A CN 102104170 A CN102104170 A CN 102104170A CN 2010106142192 A CN2010106142192 A CN 2010106142192A CN 201010614219 A CN201010614219 A CN 201010614219A CN 102104170 A CN102104170 A CN 102104170A
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- secondary battery
- positive electrode
- lithium secondary
- capacity high
- lithium
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a great-capacity high-power lithium secondary battery comprising a positive electrode, an electrolyte and a negative electrode. The great-capacity high-power lithium secondary battery is characterized in that the electrolyte contains bi-(mefluidide) lithium imide, the positive electrode is selected from a lithium-rich positive electrode material, and the negative electrode is selected from either of H2Ti12O25 or molybdenum dioxide. The invention also discloses a preparation method of the battery. The lithium secondary battery prepared by utilizing the method has high power and capacity and is suitable for lithium ion power and storage batteries in the fields of electric vehicles and new energy.
Description
Technical field
The invention belongs to the secondary lithium battery field, relate in particular to a kind of lithium secondary cell with high capacity and manufacture method thereof.
Background technology
Because the continuous exhaustion of fossil energy and environmental pollution is serious day by day, developing the alternative energy and energy-saving and emission-reduction has been trend of the times.New forms of energy such as solar energy, wind energy and electric automobile, hybrid vehicle have started climax in the world.Lithium ion battery is as the accumulation power supply of the core power supply of electric automobile and solar energy, wind energy, its research and development are significant for the development of new forms of energy, research and development to its critical material and technology are particularly important, the research and development of high power particularly of new generation, high-capacity lithium-ion power and energy-storage battery, extremely urgent especially.Because lithium ion power and energy-storage battery are in the great strategic importance of electric automobile and new energy field, no matter various countries are government or enterprise, all promoting its development, to seize the first chance of new industry with doing one's utmost.China is lithium ion battery demand big country, also is big producing country, but is not technology power.Aspect the research and development of lithium ion battery, the U.S., Japan are leading relatively, and the U.S. has remarkable advantages aspect the originality and basic research of critical material and technology; Japan is then leading aspect application technology and technology of preparing.China is basic and synchronously international aspect the research of lithium ion power and energy-storage battery, but lacks originality and independent intellectual property right, and the key technology aspect is also comparatively backward, has seriously restricted its development.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of lithium secondary battery of large-capacity high-power, and preparation method thereof.
A kind of large-capacity high-power lithium secondary battery is made up of positive electrode, electrolyte and negative electrode, contains two (fluorine sulphonyl) imines lithiums in the described electrolyte, and described positive electrode is selected for use: lithium-rich anode material, described negative electrode is selected for use: H
2Ti
12O
25Or in the molybdenum dioxide any one;
Described lithium-rich anode material is: bLi
2MnO
3(1-b) LiMO
2, the value of described b is: 0＜b＜1, described LiMO
2For: LiCo
xNi
yMn
zO
2, wherein x+y+z=1 or LiMn
2O
4Or Li
4Mn
5O
9Or Li
4Mn
5O
12In at least a.
The preparation method of above-mentioned large-capacity high-power lithium secondary battery comprises the steps:
(1), the binding agent that will contain the conductive agent of negative material active material, 0.5～15% mass ratio of 75～99% mass ratioes and 1～10% mass ratio is dissolved in and makes the negative electrode slurry in the solvent, with the Copper Foil that 9 μ m～25 μ m are thick is collector, be coated on the Copper Foil cathode size and drying, with pole piece roll-in, cut-parts, make negative plate then;
(2), the binding agent that will contain the conductive agent of positive electrode active material, 1～40% mass ratio of 59～98% mass ratioes and 1～10% mass ratio is dissolved in and makes the positive electrode slurry in the solvent, with the aluminium foil that 15 μ m～40 μ m are thick is collector, be coated on the aluminium foil anode sizing agent and drying, with pole piece roll-in, cut-parts, make positive plate then;
(3), with above-mentioned negative electrode and positive electrode add barrier film together lamination or coiling, coating or go into shell, welding, notes electrolyte, packaging process after obtain the lithium battery semi-finished product, wherein negative electrode and positive electrode are isolated by barrier film;
(4), the lithium battery semi-finished product that obtain in the step (3) are pressurizeed change into, partial volume, detection, obtain the finished product lithium battery.
Described step (1), (2) described solvent are a kind of in water, N～methyl pyrrolidone, dimethylformamide or the dimethylacetylamide.
In described step (1), (2), described binding agent is polyethylene glycol oxide, polyacrylonitrile, polymethacrylates, sodium carboxymethylcellulose, neoprene, acrylonitrile-butadiene rubber, chlorosulfonated polyethylene rubber, styrene～butadiene～styrene rubber, acrylonitrile～butadiene～styrene rubber, at least a in polytetrafluoroethylene, the polytetrafluoroethylene partially.
In described step (1), (2), described conductive agent is conductive black, electrically conductive graphite, conductive carbon nanotube and polypyrrole PPy or polyaniline PANI or polythiophene PTh or poly-at least a among benzene PPP or the poly-phenylene vinylene (ppv) PPV.
Beneficial effect body of the present invention is:
(1) the present invention uses two (fluorine sulphonyl) imines lithiums to do electrolyte, can improve the high and low temperature performance and the ionic conductance of battery greatly.
(2) the present invention adopts conducting polymer as conductive additive, not only can improve the conductivity and the cycle life of active material, can also reduce the use amount of binding agent.These conducting polymers have certain storage lithium activity, and stronger to the tolerance of expanding with heat and contract with cold, pole piece is not easy efflorescence, and macromolecule is more eager to excel in whatever one does than inorganic conductive agent to the affinity of binding agent, and the use amount of binding agent also can reduce, and provides cost savings so greatly.
(3) the present invention has adopted the storage lithium active material that is suitable for high power capacity, high-multiplying-power battery, as lithium-rich anode material bLi
2MnO
3(1-b) LiMO
2(wherein, 0＜b＜1, LiMO
2Be LiCo
xNi
yMn
zO
2, x+y+z=1 or LiMn
2O
4Or Li
4Mn
5O
9Or Li
4Mn
5O
12), H
2Ti
12O
25Or molybdenum dioxide, the making of easier realization large-capacity high-power lithium secondary battery.
(4) the present invention's increase pressure in formation process, the formation of favourable SEI film and the discharge of waste gas.
Description of drawings
Fig. 1 is the making flow chart of convoluted big capacity high rate lithium secondary battery;
Fig. 2 is the making flow chart of the big capacity high rate lithium secondary battery of laminated type.
Embodiment
Below by embodiment the present invention is specifically described.
Embodiment 1
A kind of large-capacity high-power lithium secondary battery is made up of positive electrode, electrolyte and negative electrode, contains two (fluorine sulphonyl) imines lithium LiN (SO in the described electrolyte
2F)
2, by the design of 18650 standard cells, as shown in Figure 1, concrete manufacturing process is as follows:
The preparation method of above-mentioned large-capacity high-power lithium secondary battery comprises the steps:
The H that 1. will contain 87% mass ratio
2Ti
12O
25, the conductive black of 5% mass ratio and the Kynoar of 8% mass ratio be solute, with the N-methyl pyrrolidone is that solvent is made the negative electrode slurry, make collector with the Copper Foil behind the 9 μ m, cathode size is coated onto on the positive and negative two sides of Copper Foil, after the drying, through roll-in, cut-parts, make negative plate, its compacted density is 2.1g/cm
3
The 0.5Li that 2. will contain 93% mass ratio
2MnO
30.5LiCo
0.44Ni
0.25Mn
0.31O
2, the polythiophene of 2% mass ratio, the acetylene black of 2% mass ratio, the Kynoar of 3% mass ratio is dissolved in makes the positive electrode slurry in the N-methyl pyrrolidone, with the thick aluminium foil of 16 μ m is collector, anode sizing agent is coated on the positive and negative two sides of aluminium foil, after the drying, through roll-in, cut-parts, make positive plate, its compacted density is 3.7g/cm
3
3. above-mentioned negative electrode and positive electrode are added that the polypropylene micro-pore septum reels together, successively through going into shell, welding, notes 1mol/LiN (SO
2F)
2/ EC-DMC (1: 1) solution is to obtain the lithium battery semi-finished product behind electrolyte, the packaging process, and wherein negative electrode and positive electrode are isolated by barrier film;
4. the lithium battery semi-finished product that step is obtained in 3. pressurize change into, partial volume, detection, obtain the finished product lithium battery.
After tested, 18650 battery capacities that present embodiment 1 obtains are 4.286Ah, internal resistance 19m Ω, and the voltage platform of 2.224V appears in open circuit voltage 2.457V, battery, and the capability retention of 500 circulation back batteries is 97.72%.
Embodiment 2
The large-capacity high-power lithium secondary battery of present embodiment is made up of through lamination or coiling, encapsulation positive electrode, electrolyte and negative electrode, contains two (fluorine sulphonyl) imines lithium LiN (SO in the described electrolyte
2F)
2, press the design of 50Ah cell, as shown in Figure 2, concrete manufacturing process is as follows:
The MoO that 1. will contain 90% mass ratio
2, the carbon nano-tube of 5% mass ratio, the sodium carboxymethylcellulose of 1.5% mass ratio and the chlorosulfonated polyethylene rubber of 3.5% mass ratio be solute, with the N-methyl pyrrolidone is that solvent is made the negative electrode slurry, make collector with the Copper Foil behind the 15 μ m, cathode size is coated onto on the positive and negative two sides of Copper Foil, after the drying, through roll-in, cut-parts, make negative plate, its compacted density is 4.5g/cm
3
The 0.3Li that 2. will contain 91% mass ratio
2MnO
30.7LiCo
1/3Ni
1/3Mn
1/3O
2, 5% mass ratio acetylene black, the acrylonitrile-butadiene-styrene (ABS) rubber of the polyethylene glycol oxide of 1% mass ratio and 3% mass ratio is that solute is made the positive electrode slurry, with the thick aluminium foil of 25 μ m is collector, anode sizing agent is coated on the positive and negative two sides of aluminium foil, after the drying, through roll-in, cut-parts, make positive plate, its compacted density is 3.6g/cm
3
3. above-mentioned negative electrode and positive electrode are intersected lamination with the polyethylene micropore barrier film, pass through soldering polar ear, coating, notes 1mol/LiN (SO successively
2F)
2/ EC-DMC (1: 1) solution is to obtain the lithium battery semi-finished product behind electrolyte, the packaging process, and wherein negative electrode and positive electrode are isolated by barrier film;
4. the lithium battery semi-finished product that step is obtained in 3. pressurize change into, partial volume, detection, obtain the finished product lithium battery.
After tested, the 50Ah internal resistance of cell that present embodiment 2 obtains is 2.115m Ω, and the voltage platform of 2.717V appears in open circuit voltage 2.943V, battery, and the capability retention of 500 circulation back batteries is 96.57%.
Claims (5)
1. a large-capacity high-power lithium secondary battery is made up of positive electrode, electrolyte and negative electrode, it is characterized in that: contain two (fluorine sulphonyl) imines lithiums in the described electrolyte, described positive electrode is selected for use: lithium-rich anode material, described negative electrode is selected for use: H
2Ti
12O
25Or in the molybdenum dioxide any one;
Described lithium-rich anode material is: bLi
2MnO
3(1-b) LiMO
2, the value of described b is: 0＜b＜1, described LiMO
2For: LiCo
xNi
yMn
zO
2, wherein x+y+z=1 or LiMn
2O
4Or Li
4Mn
5O
9Or Li
4Mn
5O
12In at least a.
2. the preparation method of a large-capacity high-power lithium secondary battery is characterized in that, comprises the steps:
(1), the binding agent that will contain the conductive agent of negative material active material, 0.5～15% mass ratio of 75～99% mass ratioes and 1～10% mass ratio is dissolved in and makes the negative electrode slurry in the solvent, with the Copper Foil that 9 μ m～25 μ m are thick is collector, be coated on the Copper Foil cathode size and drying, with pole piece roll-in, cut-parts, make negative plate then;
(2), the binding agent that will contain the conductive agent of positive electrode active material, 1～40% mass ratio of 59～98% mass ratioes and 1～10% mass ratio is dissolved in and makes the positive electrode slurry in the solvent, with the aluminium foil that 15 μ m～40 μ m are thick is collector, be coated on the aluminium foil anode sizing agent and drying, with pole piece roll-in, cut-parts, make positive plate then;
(3), with above-mentioned negative electrode and positive electrode add barrier film together lamination or coiling, coating or go into shell, welding, notes electrolyte, packaging process after obtain the lithium battery semi-finished product, wherein negative electrode and positive electrode are isolated by barrier film;
(4), the lithium battery semi-finished product that obtain in the step (3) are pressurizeed change into, partial volume, detection, obtain the finished product lithium battery.
3. the preparation method of large-capacity high-power lithium secondary battery according to claim 2 is characterized in that: step (1), (2) described solvent are a kind of in water, N～methyl pyrrolidone, dimethylformamide or the dimethylacetylamide.
4. according to the preparation method of the described large-capacity high-power lithium secondary battery of claim 2, it is characterized in that in step (1), (2) that described binding agent is polyethylene glycol oxide, polyacrylonitrile, polymethacrylates, sodium carboxymethylcellulose, neoprene, acrylonitrile-butadiene rubber, chlorosulfonated polyethylene rubber, styrene～butadiene～styrene rubber, acrylonitrile～butadiene～styrene rubber, at least a in polytetrafluoroethylene, the polytetrafluoroethylene partially.
5. according to the preparation method of the described large-capacity high-power lithium secondary battery of claim 2, it is characterized in that in step (1), (2) that described conductive agent is conductive black, electrically conductive graphite, conductive carbon nanotube and polypyrrole PPy or polyaniline PANI or polythiophene PTh or poly-at least a among benzene PPP or the poly-phenylene vinylene (ppv) PPV.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102368543A (en) * | 2011-11-01 | 2012-03-07 | 东莞新能源科技有限公司 | Lithium ion battery cathode and lithium ion battery therewith |
| CN102544626A (en) * | 2012-03-09 | 2012-07-04 | 天津市捷威动力工业有限公司 | Method and device for removing internal gas from laminated lithium ion battery |
| CN102778488A (en) * | 2012-07-24 | 2012-11-14 | 北京理工大学 | Randomly-combined standard single particle electrode |
| CN103022492A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing improved negative-pole graphite composite material for lithium ion battery |
| CN107359333A (en) * | 2017-07-07 | 2017-11-17 | 天津巴莫科技股份有限公司 | A kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof |
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| CN1716681A (en) * | 2004-06-30 | 2006-01-04 | 三星Sdi株式会社 | Lithium secondary battery |
| CN101409369A (en) * | 2008-11-14 | 2009-04-15 | 东莞市迈科科技有限公司 | Large-capacity high power polymer ferric lithium phosphate power cell and preparation method thereof |
| CN101679066A (en) * | 2007-03-13 | 2010-03-24 | 独立行政法人产业技术总合研究所 | New titanium oxide and manufacture method thereof and the lithium secondary battery that this titanium oxide is used as active substance |
| CN101714670A (en) * | 2008-10-02 | 2010-05-26 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery and active material for nonaqueous electrolyte secondary battery |
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2010
- 2010-12-30 CN CN2010106142192A patent/CN102104170A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1716681A (en) * | 2004-06-30 | 2006-01-04 | 三星Sdi株式会社 | Lithium secondary battery |
| CN101679066A (en) * | 2007-03-13 | 2010-03-24 | 独立行政法人产业技术总合研究所 | New titanium oxide and manufacture method thereof and the lithium secondary battery that this titanium oxide is used as active substance |
| CN101714670A (en) * | 2008-10-02 | 2010-05-26 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery and active material for nonaqueous electrolyte secondary battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102368543A (en) * | 2011-11-01 | 2012-03-07 | 东莞新能源科技有限公司 | Lithium ion battery cathode and lithium ion battery therewith |
| CN102544626A (en) * | 2012-03-09 | 2012-07-04 | 天津市捷威动力工业有限公司 | Method and device for removing internal gas from laminated lithium ion battery |
| CN102778488A (en) * | 2012-07-24 | 2012-11-14 | 北京理工大学 | Randomly-combined standard single particle electrode |
| CN103022492A (en) * | 2012-11-28 | 2013-04-03 | 上海锦众信息科技有限公司 | Method for preparing improved negative-pole graphite composite material for lithium ion battery |
| CN107359333A (en) * | 2017-07-07 | 2017-11-17 | 天津巴莫科技股份有限公司 | A kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof |
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Application publication date: 20110622 |