CN101262078A - Quickly chargeable lithium ion battery and its making method - Google Patents
Quickly chargeable lithium ion battery and its making method Download PDFInfo
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- CN101262078A CN101262078A CNA2008100527283A CN200810052728A CN101262078A CN 101262078 A CN101262078 A CN 101262078A CN A2008100527283 A CNA2008100527283 A CN A2008100527283A CN 200810052728 A CN200810052728 A CN 200810052728A CN 101262078 A CN101262078 A CN 101262078A
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- 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
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Abstract
The invention discloses a lithium-ion battery with fast charge property, which comprises an anode, a cathode, a diaphragm sandwiched between the anode and the cathode and an organic electrolyte, wherein, sub micrometer lithium titanate is used as the active substance of the cathode; one or several materials of lithium manganate (LiMn2O4), lithium iron phosphate (LiFePO4), lithium nickel cobalt oxide (LiNixCoyMzO2), ternary substance(LiNixMnxCo1-2xO2) are used as active materials of the anode, or a mixture of lithium cobalt (LiCoO2) and one of lithium manganate (LiMn2O4), lithium iron phosphate (LiFePO4), lithium nickel cobalt oxide (LiNixCoyMzO2), ternary substance(LiNixMnxCo1-2xO2) is adopted as the active materials of the anode; lithium hexafluorophosphate (LiPF6) is adopted as the electrolyte, and a multicomponent mixture of ethylene carbonate (EC), dimethylcarbonate(DMC), Ethyl Methyl Carbonate (EMC) is used as a solution. The invention also discloses a preparation method of the lithium-ion battery with fast charged property. The lithium-ion battery of the invention has excellent fast charging and discharging performance.
Description
Technical field
The present invention relates to the lithium-ion battery energy technical field, particularly relate to a kind of lithium ion battery of quickly-chargeable and the method for preparation thereof.
Background technology
Lithium-ions battery has specific energy height, voltage platform height, has extended cycle life, operating temperature range is wide, memory-less effect, characteristic such as environmentally friendly, since coming out, just obtain swift and violent development, be widely used in dual-use various portable consuming device, for example mobile phone, notebook computer, electric tool, electronic instrument etc., and beginning is applied to electric automobile, arms equipment etc. gradually.
In research and application in the past, mainly discharge performance, security performance, the storge quality of lithium ion battery are examined, the charging performance of lithium ion battery is not generally done requirement.But along with the application of lithium-ions battery in electric tool, electric motor car etc., people wish that lithium-ions battery also has good charging performance, to reduce the stand-by period of battery charge.
Lithium-ion battery system mostly is LiCoO at present
2/ polynary electrolyte system/C, the charging standard adopts first constant current charge more, and (electric current is smaller or equal to 1I
tA), back constant voltage charge, the charging interval was greater than 1 hour.Its large current charge situation is: with 10I
tThe A current charges can only charge about 30% in 5 minutes; With 5I
tThe A current charges can only charge about 50% in 10 minutes.Therefore this system to fill effect soon relatively poor, can not satisfy the requirement of electric tool, battery of electric vehicle quick charge.
Summary of the invention
In order to address the above problem, but the object of the present invention is to provide a kind of lithium ion battery and preparation method thereof with the fast charging and discharging that fills effect preferably soon.
The objective of the invention is to be achieved through the following technical solutions:
A kind of lithium ion battery of quickly-chargeable, comprise positive electrode, negative electrode, be inserted in barrier film and organic electrolyte between positive electrode and the negative electrode, the active material of wherein said negative electrode is the submicron order lithium titanate, and the active material of described positive electrode is LiMn2O4 (LiMn
2O
4), LiFePO4 (LiFePO
4), lithium nickel cobalt dioxide (LiNi
xCo
yM
zO
2) and ternary material (LiNi
xMn
xCo
1-2xO
2) in one or more or cobalt acid lithium (LiCoO
2) and wherein a kind of mixture, described electrolyte is with lithium hexafluoro phosphate (LiPF
6) be electrolyte, be solvent with the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC) and ethyl-methyl carbonic ester (EMC).
Granularity (the D of above-mentioned submicron order lithium titanate
50) less than 10 μ m, specific area is greater than 1m
2/ g.
Above-mentioned LiNi
xCo
yM
zO
2In, M is Al, Mg, Sr, Sn, Mn or Fe, 0＜X＜1,0＜Y＜1,0＜Z＜1 wherein, X+Y+Z=1; Described LiNi
xMn
xCo
1-2xO
2In, 0＜X≤0.5.
A kind of preparation method of lithium ion battery of quickly-chargeable may further comprise the steps:
1) binding agent of the conductive agent of the submicron order lithium titanate of 70%-98% weight, 1%-15% weight and 1%-10% weight is dissolved in makes cathode size in the solvent, with the thick Copper Foil of 10 μ m is collector, be coated onto on the Copper Foil cathode size and drying, make pole piece, then pole piece rolled, shear and make negative electrode;
2) binding agent of the conductive agent of the positive active material of 70%-98% weight, 1%-10% and 1%-10% is dissolved in makes anode sizing agent in the solvent, with the thick aluminium foil of 15 μ m is collector, be coated on the aluminium foil anode sizing agent and drying, make pole piece, then pole piece rolled, shear and make positive electrode;
3) adopting the polypropylene dedicated resin barrier film of lithium ion battery is battery diaphragm, and electrolyte is with LiPF
6Being electrolyte, is solvent with the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC);
4) described positive electrode (pole piece), negative electrode (pole piece) are wound into electric core with barrier film, put into battery case, inject electrolyte then and seal;
5) change into reprocessing.
In above-mentioned preparation method, the coated weight of positive and negative electrode is all less than 48mg/cm
2
Above-mentioned conductive agent is super conductive black or electrically conductive graphite.
Above-mentioned binding agent is polytetrafluoroethylene, Kynoar.
Above-mentioned solvent is N-methyl pyrrolidone, dimethylformamide or dimethylacetylamide.
The lithium ion battery of quickly-chargeable of the present invention is owing to adopted the lithium titanate (Li of submicron order
4Ti
5O
12) be negative electrode active material, with LiMn2O4 (LiMn
2O
4), LiFePO4 (LiFePO
4), lithium nickel cobalt dioxide (LiNi
xCo
yM
zO
2) and ternary material (LiNi
xMn
xCo
1-2xO
2) in a kind of be active positive electrode material, make prepared lithium ion battery have good fast charging and discharging performance.
Description of drawings
Fig. 1 is preparation method's the flow chart of the lithium ion battery of quickly-chargeable of the present invention;
Fig. 2 is in one embodiment of the present of invention, the charging curve of battery under different electric currents;
Fig. 3 is in one embodiment of the present of invention, the discharge curve of battery under different electric currents;
Fig. 4 is in one embodiment of the present of invention, 300 cyclic curves of battery;
Fig. 5 is in an alternative embodiment of the invention, the charging curve of battery under different electric currents;
Fig. 6 is in an alternative embodiment of the invention, the discharge curve of battery under different electric currents:
Fig. 7 is in an alternative embodiment of the invention, 300 cyclic curves of battery.
Embodiment
The lithium ion battery of quickly-chargeable of the present invention comprises: positive electrode, negative electrode, be inserted in barrier film and organic electrolyte between positive electrode and the negative electrode, wherein, the active material of negative electrode is the submicron order lithium titanate, and the active material of positive electrode is LiMn2O4 (LiMn
2O
4), LiFePO4 (LiFePO
4), lithium nickel cobalt dioxide (LiNi
xCo
yM
zO
2) and ternary material (LiNi
xMn
xCo
1-2xO
2) in one or more or cobalt acid lithium (LiCoO
2) and wherein a kind of mixture, described electrolyte is with lithium hexafluoro phosphate (LiPF
6) be electrolyte, be solvent with the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC) and ethyl-methyl carbonic ester (EMC).
Wherein, the granularity (D of above-mentioned submicron order lithium titanate
50) less than 10 μ m, specific area is greater than 1m
2/ g.
Preferably, the active material of positive electrode is a LiMn2O4.
The preparation method of the lithium ion battery of quickly-chargeable of the present invention may further comprise the steps:
1) binding agent of the conductive agent of the submicron order lithium titanate of 70%-98% weight, 1%-15% weight and 1%-10% weight is dissolved in makes cathode size in the solvent, with the thick Copper Foil of 10 μ m is collector, be coated onto on the Copper Foil cathode size and drying, make pole piece, then pole piece rolled, shear and make negative electrode;
2) binding agent of the conductive agent of the LiMn2O4 of 70%-98% weight, 1%-10% and 1%-10% is dissolved in makes anode sizing agent in the solvent, with the thick aluminium foil of 15 μ m is collector, be coated on the aluminium foil anode sizing agent and drying, make pole piece, then pole piece rolled, shear and make negative electrode;
3) adopting the polypropylene dedicated resin barrier film of lithium ion battery is battery diaphragm, and electrolyte is with LiPF
6Being electrolyte, is solvent with the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC);
4) described positive electrode (pole piece), negative electrode (pole piece) are wound into electric core with barrier film, put into battery case, inject electrolyte then and seal;
5) change into reprocessing.
The coated weight of above-mentioned negative electrode is less than 48mg/cm
2, the coated weight of positive electrode is less than 48mg/cm
2
Above-mentioned conductive agent is super conductive black or electrically conductive graphite, and above-mentioned binding agent is polytetrafluoroethylene, Kynoar or polymer resin.
Above-mentioned solvent is N-methyl pyrrolidone, dimethylformamide or dimethylacetylamide, preferably the N-methyl pyrrolidone.
Preparation method to the lithium ion battery of quickly-chargeable of the present invention is elaborated below in conjunction with specific embodiment.
(as follows) by mass percentage, 85% positive active material LiMn2O4,5% super conductive black, 10% binding agent Kynoar is made solvent with the N-methyl pyrrolidone, the furnishing lotion, make collector with the thick aluminium foil of 15 μ m, be coated on the aluminium foil creme and drying.
With pole piece roll, shearing, soldering polar ear make positive plate, electrode density is 2.9g/cm
3
Negative material submicron order lithium titanate (D with 80%
50Be 0.185 μ m, specific area is 5.2m
2/ g) with 8% super conductive black, 12% binding agent Kynoar, make solvent furnishing paste with the N-methyl pyrrolidone, make collector with the thick Copper Foil of 10 μ m, creme is coated onto on the Copper Foil and dry.
With pole piece roll, shearing, soldering polar ear make negative plate, electrode density is 3.8g/cm
3
Adopting the special-purpose barrier film of acrylic resin lithium ion battery is battery diaphragm.
Electrolyte is selected LiPF for use
6, dicyandiamide solution is the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC) etc.
Positive electrode (pole piece), negative electrode (pole piece) are wound into electric core with barrier film, after the shaping, put into battery case, inject electrolyte then and seal.
It is changed into reprocessing.
Be prepared into the ICP053048 lithium ion rectangular cell, with the 10ItA current charges, 5 minutes chargeable 80.1%.
Embodiment 2
Difference from Example 1, the ratio of positive-material lithium manganate, super conductive black, binding agent is respectively in the positive electrode: 90%, 3%, 7%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 87%, 5%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 82.8%.
Charge and discharge curve and the cyclic curve of made battery under different electric currents seen Fig. 2～Fig. 4.
Embodiment 3
Difference from Example 1, the ratio of positive-material lithium manganate, super conductive black, binding agent is respectively in the positive electrode: 93%, 2%, 5%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 90%, 3%, 7%.
The 10ItA current charges of the lithium ion battery that above-mentioned 3 embodiment make, 10ItA discharge and 300 loop-around datas see Table 1.
The battery performance of table 1 embodiment 1-embodiment 3
| Sequence number | Battery average size mAh | 10ItA, the 5min % that charges | The 10ItA % that discharges | 300 circulation % |
| |
330 | 80.1 | 81.3 | 81.2 |
| Embodiment 2 | 400 | 82.8 | 85.6 | 85.7 |
| Embodiment 3 | 420 | 80.9 | 82.7 | 84.8 |
Embodiment 4:
Difference from Example 1, conductive agent adopts electrically conductive graphite; The ratio of LiMn2O4, electrically conductive graphite, binding agent is respectively in the positive electrode: 89%, 4%, 7%; The ratio of negative material submicron order lithium titanate, electrically conductive graphite, binding agent is respectively in the negative electrode: 86%, 6%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 81.2%.
Embodiment 5:
Difference from Example 1, active material adopts LiFePO4 in the positive electrode; The ratio of LiFePO4, super conductive black, binding agent is respectively in the positive electrode: 90%, 3%, 7%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 87%, 5%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 82.9%.
Charge and discharge curve and the cyclic curve of made battery under different electric currents seen Fig. 5～Fig. 7.
The battery performance of table 2 embodiment 4-5
| Sequence number | Battery average size mAh | 10ItA, the 5min % that charges | The 10ItA % that discharges | 300 |
| Embodiment | ||||
| 4 | 385 | 81.2 | 80.5 | 82.6 |
| Embodiment 5 | 360 | 82.9 | 86.6 | 90.1 |
Embodiment 6
Difference from Example 1, active material adopts lithium nickel cobalt dioxide material (LiNi in the positive electrode
0.8Co
0.15Al
0.05O
2); The ratio of lithium nickel cobalt dioxide, super conductive black, binding agent is respectively in the positive electrode: 90%, 3%, 7%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 87%, 5%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 80.5%.
Embodiment 7
Difference from Example 1, active material adopts ternary material (LiNi in the positive electrode
1/3Co
1/3Mn
1/3O
2); The ratio of lithium nickel cobalt dioxide, super conductive black, binding agent is respectively in the positive electrode: 90%, 3%, 7%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 87%, 5%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 82.4%.
Embodiment 8
Difference from Example 1, active material adopts cobalt acid lithium (LiCoO in the positive electrode
2) and ternary material (LiNi
1/3Co
1/3Mn
1/3O
2) composite material (mixing) by 9: 1; The ratio of composite material, super conductive black, binding agent is respectively in the positive electrode: 90%, 3%, 7%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 87%, 5%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 83.2%.
Embodiment 9
Difference from Example 1, active material adopts cobalt acid lithium (LiCoO in the positive electrode
2) with the composite material (mixing) of LiMn2O4 by 9: 1; The ratio of composite material, super conductive black, binding agent is respectively in the positive electrode: 90%, 3%, 7%; The ratio of negative material submicron order lithium titanate, super conductive black, binding agent is respectively in the negative electrode: 87%, 5%, 8%.
Be prepared into the rectangular lithium ion battery of ICP053048, with the 10ItA current charges, 5 minutes chargeable 82.6%.
By the data among accompanying drawing and the table 1-2 as seen, lithium ion battery of the present invention is with 10I
tThe current charges of A can be charged to more than 80% of battery capacity in 5 minutes; With 10I
tThe current discharge of A can be emitted more than 80% of battery capacity; Circulating, battery capacity keeps having good fast charging and discharging performance more than 80% after 300 times.
Claims (8)
1. the lithium ion battery of a quickly-chargeable, comprise positive electrode, negative electrode, be inserted in barrier film and organic electrolyte between positive electrode and the negative electrode, it is characterized in that: the active material of described negative electrode is the submicron order lithium titanate, and the active material of described positive electrode is LiMn2O4 (LiMn
2O
4), LiFePO4 (LiFePO
4), lithium nickel cobalt dioxide (LiNi
xCo
yM
zO
2) and ternary material (LiNi
xMn
xCo
1-2xO
2) in one or more or cobalt acid lithium (LiCoO
2) and wherein a kind of mixture, described electrolyte is with lithium hexafluoro phosphate (LiPF
6) be electrolyte, be solvent with the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC) and ethyl-methyl carbonic ester (EMC).
2. lithium ion battery according to claim 1 is characterized in that: the granularity (D of described submicron order lithium titanate
50) less than 10 μ m, specific area is greater than 1m
2/ g.
3. lithium ion battery according to claim 1 is characterized in that: described LiNi
xCo
yM
zO
2In, M is Al, Mg, Sr, Sn, Mn or Fe, 0＜X＜1,0＜Y＜1,0＜Z＜1 wherein, X+Y+Z=1; Described LiNi
xMn
xCo
1-2xO
2In, 0＜X≤0.5.
4. the preparation method of the lithium ion battery of a quickly-chargeable may further comprise the steps:
1) binding agent of the conductive agent of the submicron order lithium titanate of 70%-98% weight, 1%-15% weight and 1%-10% weight is dissolved in makes cathode size in the solvent, with the thick Copper Foil of 10 μ m is collector, be coated onto on the Copper Foil cathode size and drying, make pole piece, then pole piece rolled, shear and make negative electrode;
2) binding agent of the conductive agent of the positive active material of 70%-98% weight, 1%-10% and 1%-10% is dissolved in makes anode sizing agent in the solvent, with the thick aluminium foil of 15 μ m is collector, be coated on the aluminium foil anode sizing agent and drying, make pole piece, then pole piece rolled, shear and make positive electrode;
3) adopting the polypropylene dedicated resin barrier film of lithium ion battery is battery diaphragm, and electrolyte is with LiPF
6Being electrolyte, is solvent with the multicomponent mixture of vinyl carbonate (EC), dimethyl carbonate (DMC), ethyl-methyl carbonic ester (EMC);
4) described positive electrode (pole piece), negative electrode (pole piece) are wound into electric core with barrier film, put into battery case, inject electrolyte then and seal;
5) change into reprocessing.
5. preparation method according to claim 4 is characterized in that: the coated weight of positive and negative electrode is all less than 48mg/cm
2
6. preparation method according to claim 4 is characterized in that: described conductive agent is super conductive black or electrically conductive graphite.
7. preparation method according to claim 4 is characterized in that: described binding agent is polytetrafluoroethylene, Kynoar.
8. preparation method according to claim 4 is characterized in that: described solvent is N-methyl pyrrolidone, dimethylformamide or dimethylacetylamide.
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| CN102299368A (en) * | 2011-08-03 | 2011-12-28 | 珠海锂源动力科技有限公司 | Lithium ion battery with lithium titanate and lithium nickel cobalt oxide system and preparation method thereof |
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