CN102820487A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN102820487A CN102820487A CN2012102560564A CN201210256056A CN102820487A CN 102820487 A CN102820487 A CN 102820487A CN 2012102560564 A CN2012102560564 A CN 2012102560564A CN 201210256056 A CN201210256056 A CN 201210256056A CN 102820487 A CN102820487 A CN 102820487A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 91
- 238000010277 constant-current charging Methods 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000007600 charging Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 3
- 230000008961 swelling Effects 0.000 abstract 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000010280 constant potential charging Methods 0.000 abstract 1
- 238000005562 fading Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000956 alloy Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000006258 conductive agent Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000011257 shell material Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 6
- 239000006245 Carbon black Super-P Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 239000006183 anode active material Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000010278 pulse charging Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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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
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery. Formation of the lithium ion battery is realized through the following steps at a temperature of -20 to 60 DEG C: subjecting the lithium ion battery which has been infiltrated by injection liquid to pulsed constant current charging until the voltage of the lithium ion battery reaches a designated value which is in a range of 3.4 to 4.2 V; carrying out constant voltage charging on the lithium ion battery until the current of the lithium ion battery reaches a designated value which is 0.05 C; and subjecting the lithium ion battery to constant current discharging, wherein the value of discharging voltage is in a range of 3.0 to 2.0 V and the value of discharging current is in a range of 0.01 to 2.0 C. According to the invention, a formation manner of pulsed constant current charging is adopted for the silicon carbon material negative electrode lithium ion battery, and thus, swelling of the volume of the battery is effectively alleviated and battery deformation and cracking and wrinkling of pole pieces caused by swelling of the volume are effectively alleviated, thereby further alleviating capacity fading.
Description
Technical field
The present invention relates to the battery technology field, especially relate to a kind of lithium ion battery.
Background technology
The kind of battery is a lot of on the market at present, and lithium ion battery is widely used in fields such as electronics, traffic, the energy owing to advantages such as having high-energy-density, high output voltage, high-output power.Along with the development of new forms of energy industry, the exploitation of high-energy-density, high-output power battery, the direction of alloy anode high-capacity battery development of new generation because of its high power capacity, high discharge platform, excellent security performance become.Yet, adopting this alloy material in the battery formation process, to be accompanied by enormousness and change, the internal stress of alloy material is very big; Cause peeling off of electrode material easily; The diaphragm internal resistance enlarges markedly, and the material surface that exposes simultaneously constantly forms new SEI film, and then causes the cycle performance of battery poor.In addition, cause battery container to expand, be out of shape easily.
In the conventional battery manufacture process, generally adopt following battery chemical synthesis technology: battery liquid-filling soaks into the back and adopts the electric current of 0.01-1.0 C to carry out constant current charge, and charging voltage is 3.4-4.2V; Let battery get into the constant voltage charge stage again, sustaining voltage is between 3.4-4.2V, and this moment, electric current reduced gradually, then promptly stops charging when charging current is reduced to 0.001-0.02C.Shelve then, discharge flow path.
Above-mentioned this battery chemical synthesis technology, for the lithium ion battery of alloy anode, the volumetric expansion in the initial charge process of the negative electrode material layer on the pole piece continues accumulation; Cause structure obviously to be destroyed; Like pole piece distortion, battery electrical property significantly worsens, even causes short circuit, analyses safety problem such as lithium.
Summary of the invention
Main purpose of the present invention is to provide a kind of lithium ion battery, improves in the lithium ion battery alloy negative pole formation process problem that battery pole piece expands and is out of shape.
The present invention proposes a kind of lithium ion battery, under-20 ~ 60oC environment, changes into through following steps:
Step 1, the lithium ion battery after fluid injection soaked into carry out the pulse constant current charging, reach designated value until voltage, and the designated value scope of said voltage is 3.4-4.2V;
Step 2, lithium ion battery is carried out constant voltage charge, reach designated value until electric current, the designated value scope of said electric current is 0.05C;
Step 3, lithium ion battery is carried out constant-current discharge, discharge voltage value scope is 3.0-2.0V, and the discharge current value scope is 0.01-2.0C.
Preferably, following steps are carried out in the circulation that is specially of in the said step 1 lithium ion battery being carried out pulse constant current charging:
Lithium ion battery is carried out constant current charge T with current value I
1Carry out constant current charge T with current value I+△ I again
2Repeat successively, reach designated value up to charging voltage, the designated value scope of said voltage is 3.4-4.2V; Said current value I scope is 0.01-1.0C, and said △ I scope is 0.05-5.0C, said T
1Scope is 100ms-3600s; Said T
2Be 100 μ s-10s.
Preferably, the negative active core-shell material of said lithium ion battery is a Si-C composite material, and this Si-C composite material is by carbon phase material and the silicon composite material formed of material mutually.
Preferably, said carbon phase material comprises: any one or more than one mixing in indefinite form carbon, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, Graphene, CNT, the carbon fiber; Said silicon phase material comprises: elemental silicon, Si oxide (SiO
x), any one or more than one mixing in siliceous solid solution or the silicon intermetallic compound.
Preferably, in the said step 1 lithium ion battery is carried out being specially of pulse constant current charging:
Lithium ion battery is carried out constant current charge T with current value I
1Carry out constant current charge T with current value I+△ I again
2Carry out constant current charge T with current value I then
1Again with current value I+△ I-I
0Carry out constant current charge T
2And the like, the n subpulse begins lithium ion battery is carried out constant current charge T with current value I
1, again with current value I+△ I-(n-1) I
0Carry out constant current charge T
2, as I+ △ I-(n-1) I
0During≤I, then carry out constant current charge with current value I, reach designated value until charging voltage, said designated value scope is 3.4-4.2V; Said current value I scope is 0.01-0.2C, and said △ I scope is 0.05-5.0C, said I
0Scope is 0.0-0.5C; Said T
1Scope is 100ms-3600s, said T
2Be 100 μ s-10s.
Preferably, in the said step 2 lithium ion battery is carried out constant voltage charge and reach designated value until charging current; Wherein the constant voltage value is a voltage designated value in the step 1, and scope is 3.4-4.2V.
Lithium ion battery provided by the present invention adopts lithium ion battery is carried out the pulse constant current charging, carries out constant voltage charge again, and then lithium ion battery is carried out the mode of constant-current discharge, can effectively slow down the battery pole piece accumulation of expanding, and prevents pole piece cracking, wrinkling; And then slow down the battery loop attenuation.
Description of drawings
Fig. 1 is to the electric current and the time chart of battery constant-current pulse charging in the chemical synthesizing method of lithium ion battery of the present invention;
Fig. 2 is to battery current the successively decrease electric current and the time chart of pulse current charge in the chemical synthesizing method of lithium ion battery of the present invention.
The realization of the object of the invention, functional characteristics and advantage will combine embodiment, further specify with reference to accompanying drawing.
Embodiment
Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Lithium ion battery provided by the present invention under-20 ~ 60oC environment, changes into through following steps:
Step 1, the lithium ion battery after fluid injection soaked into carry out the pulse constant current charging, reach designated value until voltage, and the designated value scope of said voltage is 3.4-4.2V;
Step 2, lithium ion battery is carried out constant voltage charge, reach designated value until electric current, the designated value of said electric current is 0.05C;
Step 3, lithium ion battery is carried out constant-current discharge, discharge voltage value scope is 4.5-3.0V, and the discharge current value scope is 0.01-2.0C.
Further, referring to Fig. 1, following steps are carried out in the circulation that is specially of in the said step 1 lithium ion battery being carried out pulse constant current charging, and reach designated value up to cell voltage, and said designated value scope is 3.4-4.2V:
Lithium ion battery is carried out constant current charge T with current value I
1Carry out constant current charge T with current value I+△ I again
2Repeat successively, reach designated value up to charging voltage, the designated value scope of said voltage is 3.4-4.2V; Said current value I scope is 0.01-1.0C, and said △ I scope is 0.05-5.0C, said T
1Scope is 100ms-3600s; Said T
2Be 100 μ s-10s.
Further, referring to Fig. 2, in the said step 1 lithium ion battery is carried out the pulse constant current charging and can also specifically adopt following steps:
Lithium ion battery is carried out constant current charge T with current value I
1Carry out constant current charge T with big current value I+△ I again
2Carry out constant current charge T with little current value I then
1Again with current value I+△ I-I
0Carry out constant current charge T
2And the like, the n subpulse begins lithium ion battery is carried out constant current charge T with current value I
1, again with current value I+△ I-(n-1) I
0Carry out constant current charge T
2, as I+ △ I-(n-1) I
0≤I, then current value I is carried out constant current charge, reaches designated value until charging voltage, and said designated value scope is 3.4-4.2V; Said current value I scope is 0.01-0.2C, and said △ I scope is 0.05-5.0C, said I
0Scope is 0.01-0.5C; Said T
1Scope is 100ms-3600s, said T
2Be 100 μ s-10s.
Below to provide concrete embodiment and Comparative Examples that lithium ion battery of the present invention is further described.
Embodiment 1
One, makes lithium ion battery
(1), makes anode pole piece
According to the cobalt acid lithium of mass percent meter with 80-98%, the conductive agent of 0.5-10%, the binding agent mixing formation mixture of 1.5-10%, and in this mixture, add solvent; N-methyl pyrrolidone or dimethylformamide solvent stir the slurry that furnishing mixes under 2000-6000 rev/min condition; Made slurry is coated on the thick aluminum foil current collector of 10-50 μ m, with aluminum foil current collector through super-dry, roll-in, operation such as cut and be made into anode pole piece.Wherein, said conductive agent be following component one or more: acetylene black, Super-P, CNT, carbon fiber, Graphene, amorphous carbon.Binding agent is selected from one or more in polytetrafluoroethylene, Kynoar, the butadiene-styrene rubber in the said binder solution, and the solvent in the binder solution is selected from one or more in acetone, N-methyl pyrrolidone, oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO), MEK, the ethyl acetate.
(2), make cathode pole piece
By mass percentage with the alloy anode active material of 80-98%, the conductive agent of 1.5-10%, the binding agent mixing formation mixture of 0.5-10% adds solvent in this mixture, and stirs the slurry that furnishing mixes; The slurry of made is coated on the thick Copper Foil collector of 8-50 μ m, with the Copper Foil collector through drying, roll-in, operation such as cut and process cathode pole piece.Wherein, said alloy anode active material is the Si carbon-base alloy material, this Si carbon-base alloy material comprise any carbonizable substance, with the composite material of silicon matter combination, or the novel substance that forms.Said carbonizable substance comprises: any one or more than one mixing in indefinite form carbon, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, Graphene, CNT, the carbon fiber; Said silicon comprises mutually: elemental silicon, Si oxide (SiO
x), any one or more than one mixing in siliceous solid solution or the silicon intermetallic compound.Said conductive agent be following component one or more: acetylene black, Super-P, CNT, carbon fiber, Graphene, amorphous carbon.Said binding agent is a kind of of following component: one or more in polytetrafluoroethylene, Kynoar, the butadiene-styrene rubber.Said solvent can be selected from one or more in water, acetone, N-methyl pyrrolidone, oxolane, dimethyl sulfoxide (DMSO), MEK, the ethyl acetate.
(3), make the soft-package battery core
Adopting thickness is that acrylic resin and the polyvinyl resin composite membrane of 10-30 μ m is as barrier film; As electrolyte solvent, electrolyte lithium salt adopts LiPF with the ternary mixture of EC/DMC/EMC (volume ratio is 1:1:1)
6, concentration is 1 mol.Behind the positive and negative electrode pole piece soldering polar ear that branch is cut, the barrier film that cuts with branch is wound into battery, is encapsulated in the aluminum plastic film; Through after the vacuumize, inject electrolyte, then through Vacuum Package, leave standstill, cold and hot pressure, change into, operation such as two envelopes is made into lithium ion soft-package battery core.
Two, carry out the lithium ion soft-package battery and change into processing
Step a, constant current charge stage: in temperature is under the environment of 45oC, and 1.-2. circulation carries out following steps, is 3.85V until voltage: 1. carried out constant current charge 1 minute with said battery with the electric current of 0.05C; 2. adopt the electric current constant current charge 100ms of above-mentioned charging current 2C.
Step b, constant voltage charge stage: in temperature is under the environment of 45oC, and the 3.85V constant voltage charge is 0.05C until electric current;
Step c, constant-current discharge stage: in temperature is under the environment of 45oC, carries out constant-current discharge with said lithium ion battery with the electric current of 0.2C, is 3.0V until voltage.
Carry out above-mentioned steps a to c, change into end.
Embodiment 2
One, makes lithium ion battery
It is consistent with the foregoing description 1 with technological process to make the material that lithium ion battery adopted in the present embodiment.
Two, carry out the lithium ion soft-package battery and change into processing
Step a, constant current charge stage: in temperature is under the environment of 45oC, carries out following steps: (1), lithium ion battery is carried out constant current charge 600s with current value I; Carry out constant current charge 100 μ s with current value I+△ I again; (2), carry out constant current charge 600s with current value I; Again with current value I+△ I-I
0Carry out constant current charge 100 μ s; (3), carry out constant current charge 600s with current value I; Again with current value I+△ I-(n-1) I
0Advance (n is 3) row constant current charge 100 μ s; And the like, until I+ △ I-(n-1) I
0During≤I, then carry out constant current charge with current value I, reaching voltage until charging voltage is 3.85V.Wherein, in this enforcement, said current value I is 0.1C, and said △ I is 5.0C, said I
0Be 0.1C.
Step b, constant voltage charge stage: in temperature is under the environment of 45oC, and the 3.85V constant voltage charge is 0.05C until electric current;
Step c, constant-current discharge stage: in temperature is under the environment of 45oC, carries out constant-current discharge with said lithium ion battery with the electric current of 0.2C, is 3.0V until voltage.
Carry out above-mentioned steps a to c, change into end.
Comparative Examples 1
One, makes lithium ion battery
It is consistent with the foregoing description 1 with technological process to make the material that lithium ion battery adopted in this Comparative Examples.
Two, carry out the lithium ion soft-package battery and be standardized into processing
Step a, constant current charge stage: carrying out constant current charge with said battery with the electric current of 0.05 multiplying power, is 3.85V until voltage.
Step b, constant-current discharge stage: shelve, discharge flow path.
After changing into end, the battery performance parameter of test implementation example 1, embodiment 2 and Comparative Examples 1, test result is referring to table 1.Disassemble the battery after embodiment 1, embodiment 2 and Comparative Examples 1 change into, control cell core thickness changes into the back to be changed, and the state of checking cathode pole piece.The technology that wherein adopts embodiment 1 and embodiment 2 to provide changes into battery; Battery changes into back thickness to be increased less than 8%; Cathode pole piece is only micro-wrinkling. and adopt the prior standard chemical synthesis technology to change into battery; Battery changes into back thickness to be increased above 20%, and cathode pole piece obviously ftractures, and is seriously wrinkling.After the test battery 300 week circulation, capability retention enforcement 1 and embodiment 2 are all greater than 85%, and comparative example's 1 circulation conservation rate closely is 47.6%.
Table 1:
Embodiment 3
One, makes the aluminum hull lithium ion battery
(1), makes anode pole piece
According to the LiFePO 4 of mass percent meter with 80-98%, the conductive agent of 0.5-10%, the binding agent mixing formation mixture of 1.5-10%; In this mixture, add solvent; Under 2000-6000 rev/min of condition, stir the slurry that furnishing mixes; Made slurry is coated on the thick aluminum foil current collector of 10-50 μ m, with aluminum foil current collector through super-dry, roll-in, operation such as cut and be made into anode pole piece; Wherein, said conductive agent be following component one or more: acetylene black, Super-P, CNT, carbon fiber, Graphene, amorphous carbon.Binding agent is selected from one or more in polytetrafluoroethylene, Kynoar, the butadiene-styrene rubber in the said binder solution, and the solvent in the binder solution is selected from one or more in acetone, N-methyl pyrrolidone, oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO), MEK, the ethyl acetate.
(2), make cathode pole piece
By mass percentage with the alloy anode active material of 80-98%, the conductive agent of 3-11%, the binding agent mixing formation mixture of 0.5-11% adds solvent in this mixture, and stirs the slurry that furnishing mixes; The slurry of made is coated on the thick Copper Foil collector of 8-25um, with the Copper Foil collector through drying, roll-in, technology such as cut and process cathode pole piece.Said alloy anode active material is the silicon-carbon alloy material, and said silicon-carbon alloy material 100 parts of meters by weight comprises following component: 80-98 part carborundum active material, 1.5-10 part conductive agent and 0.5-10 part binding agent.Said conductive agent be following component one or more: acetylene black, Super-P, CNT, carbon fiber, Graphene, amorphous carbon.Said binding agent is a kind of of following component: one or more in polytetrafluoroethylene, Kynoar, the butadiene-styrene rubber.Said solvent can be selected from one or more in water, acetone, N-methyl pyrrolidone, oxolane, dimethyl sulfoxide (DMSO), MEK, the ethyl acetate.
(3), make aluminum-shell battery
Adopting thickness is that acrylic resin and the polyvinyl resin composite membrane of 10-30 μ m is as barrier film; Ternary mixture with EC/DMC/EMC (volume ratio is 1:1:1) is the electrolyte solvent system, and electrolyte lithium salt adopts LiPF
6, concentration is 1 mol.Behind the positive and negative plate soldering polar ear that branch is cut, the barrier film that cuts with branch is wound into battery, puts into shell then, and shell and cover plate are used laser welded seal, injects the electrolyte sealing then and changes into, and sealing, partial volume are processed aluminum-shell battery.
Two, carry out the lithium ion aluminum-shell battery and change into processing
Step a, constant current charge stage: in temperature is under the environment of 60oC, and 1.-2. following steps are carried out in circulation is 3.4V until voltage: 1. carried out constant current charge 1 hour with said battery with the electric current of 0.01C; 2. adopt the electric current constant current charge 300 μ s of above-mentioned charging current 1C.
Step b, constant voltage charge stage: in temperature is under the environment of 60oC, and the 3.4V constant voltage charge is 0.05C until electric current;
Step c, constant-current discharge stage: in temperature is under the environment of 60oC, carries out constant-current discharge with said lithium ion battery with the electric current of 0.2C, is 2.5V until voltage.
Carry out above-mentioned steps a to c, change into end.
Embodiment 4
One, makes lithium ion battery
It is consistent with the foregoing description 3 with technological process to make the material that lithium ion battery adopted in this Comparative Examples.
Two, carry out the lithium ion aluminum-shell battery and change into processing
Step a, constant current charge stage: in temperature is under the environment of 60oC, carries out following steps: (1), lithium ion battery is carried out constant current charge 3600s with current value I; Carry out constant current charge 500 μ s with current value I+△ I again; (2), carry out constant current charge 3600s with current value I; Again with current value I+△ I-I
0Carry out constant current charge 500 μ s; (3), carry out constant current charge 3600s with current value I; Again with current value I+△ I-(n-1) I
0Advance (n is 3) row constant current charge 500 μ s; And the like, until I+ △ I-(n-1) I
0During≤I, then carry out constant current charge with current value I, reaching voltage until charging voltage is 4.2V.Wherein, in this enforcement, said current value I is 0.2C, and said △ I is 3.5C, said I
0Be 0.01C.
Step b, constant voltage charge stage: in temperature is under the environment of 45oC, the 4.2V constant voltage charge, until electric current less than 0.05C.
Step c, constant-current discharge stage: in temperature is under the environment of 45oC, carries out constant-current discharge with said lithium ion battery with the electric current of 0.2C, is 2.5V until voltage.
Carry out above-mentioned steps a to c, change into end.
Comparative Examples 2
One, makes lithium ion battery
It is consistent with the foregoing description 3 with technological process to make the material that lithium ion battery adopted in this Comparative Examples.
Two, carry out the lithium ion soft-package battery and be standardized into processing
Step a, be under the environment of 60oC in temperature, the constant current charge stage: carrying out constant current charge with said battery with the electric current of 0.05C, is 3.4V until voltage.
Step b, constant-current discharge stage: shelve, 0.2C is discharged to 2.5V then.
After changing into end, the battery performance parameter of test implementation example 3, embodiment 4 and Comparative Examples 2, test result is referring to table 2.Disassemble the battery after embodiment 3, embodiment 4 and Comparative Examples 2 change into, control cell core thickness changes into the back to be changed, and the state of checking cathode pole piece.The technology that wherein adopts embodiment 3 and embodiment 4 to provide changes into battery, and battery changes into back thickness to be increased less than 5%, and cathode pole piece is only micro-wrinkling.And adopt the prior standard chemical synthesis technology to change into battery, and battery changes into back thickness increase and reaches 9.5%, and cathode pole piece obviously ftractures, and is seriously wrinkling.
Table 2:
Data by table 2 can be known: the technology that adopts embodiment 3 and embodiment 4 to provide changes into battery, and battery changes into back thickness to be increased less than 4.5%, and cathode pole piece is only micro-wrinkling; And adopt the prior standard chemical synthesis technology to change into battery, and battery changes into back thickness to be increased above 6%, and cathode pole piece obviously ftractures, and is seriously wrinkling.
Embodiment 5
One, makes cylinder (18650) lithium ion battery
(1), makes anode pole piece
According to the nickel manganese cobalt acid lithium of mass percent meter with 80-98%, the conductive agent of 1.5-10%, the binding agent mixing formation mixture of 0.5-10%; In this mixture, add solvent; Under 2000-6000 rev/min condition, stir the slurry that furnishing mixes; Made slurry is coated on the thick aluminum foil current collector of 10-50 μ m, with aluminum foil current collector through super-dry, roll-in, operation such as cut and be made into anode pole piece; Wherein, said conductive agent be following component one or more: acetylene black, Super-P, CNT, carbon fiber, Graphene, amorphous carbon.Binding agent is selected from one or more in polytetrafluoroethylene, Kynoar, the butadiene-styrene rubber in the said binder solution, and the solvent in the binder solution is selected from one or more in acetone, N-methyl pyrrolidone, oxolane, dimethyl formamide, dimethyl sulfoxide (DMSO), MEK, the ethyl acetate. (2), making cathode pole piece
By mass percentage with the alloy anode active material of 80-98%, the conductive agent of 1.5-10%, the binding agent mixing formation mixture of 0.5-10% adds solvent in this mixture, and stirs the slurry that furnishing mixes; The slurry of made is coated on the thick Copper Foil collector of 8-25 μ m, with the Copper Foil collector through drying, roll-in, technology such as cut and process cathode pole piece.Said alloy anode active material is the silicon-carbon alloy material, and said silicon-carbon alloy material 100 parts of meters by weight comprises following component: 80-98 part silicon-carbon alloy active material, 1.5-10 part conductive agent, 1.5-10 part binding agent.Said conductive agent be following component one or more: acetylene black, Super-P, CNT, carbon fiber, Graphene, amorphous carbon.Said binding agent is a kind of of following component: one or more in polytetrafluoroethylene, Kynoar, the butadiene-styrene rubber.Said solvent can be selected from one or more in water, acetone, N-methyl pyrrolidone, oxolane, dimethyl sulfoxide (DMSO), MEK, the ethyl acetate.
(3), make cylindrical battery
Adopting thickness is that acrylic resin and the polyvinyl resin composite membrane of 10-30 μ m is as barrier film; Ternary mixture with EC/DMC/EMC (volume ratio is 1:1:1) is the electrolyte solvent system, and electrolyte lithium salt adopts LiPF
6, concentration is 1 mol.Behind the positive and negative plate soldering polar ear that branch is cut, the barrier film that cuts with branch is wound into battery, puts into shell then, injects electrolyte, and after leaving standstill, top seal changes into, and partial volume is processed cylindrical battery.
Two, carry out lithium ion cylinder battery and change into processing
Step a, constant current charge stage: in temperature is under the environment of 20oC, and 1.-2. following steps are carried out in circulation is 4.0V until voltage: 1. carry out constant current charge 1800s with said battery with the electric current of 0.01C; 2. adopt the electric current constant current charge 10s of above-mentioned charging current 0.06C.
Step b, constant voltage charge stage: in temperature is under the environment of 20oC, and the 4.0V constant voltage charge is 0.05C until electric current.
Step c, constant-current discharge stage: in temperature is under the environment of 20oC, carries out constant-current discharge with said lithium ion battery with the electric current of 0.2C, is 3.0V until voltage.
Carry out above-mentioned steps a to c, change into end.
Embodiment 6
One, makes lithium ion battery
It is consistent with the foregoing description 3 with technological process to make the material that lithium ion battery adopted in this Comparative Examples.
Two, carry out lithium ion cylinder battery and change into processing
Step a, constant current charge stage: in temperature be-environment of 20oC under, carry out following steps: (1), lithium ion battery is carried out constant current charge 100 ms with current value I; Carry out constant current charge 10s with current value I+△ I again; (2), carry out constant current charge 100 ms with current value I; Again with current value I+△ I-I
0Carry out constant current charge 10s; (3), carry out constant current charge 100 ms with current value I; Again with current value I+△ I-(n-1) I
0Advance (n is 3) row constant current charge 10s; And the like, until I+ △ I-(n-1) I
0During≤I, then carry out constant current charge with current value I, reaching voltage until charging voltage is 4.0V.Wherein, in this enforcement, said current value I is 0.1C, and said △ I is 0.05C, said I
0Be 0.001C.
Step b, constant voltage charge stage: in temperature be-environment of 20oC under, the 4.0V constant voltage charge, until electric current less than 0.05C;
Step c, constant-current discharge stage: in temperature be-environment of 20oC under, carry out constant-current discharge with said lithium ion battery with the electric current of 0.2C, be 3.0V until voltage.
Above-mentioned steps a to c is carried out in circulation, changes into end.
Comparative Examples 3
One, makes cylindrical lithium ion battery
It is consistent with the foregoing description 5 with technological process to make the material that lithium ion battery adopted in this Comparative Examples.
Two, carry out lithium ion cylinder battery and be standardized into processing
Step a, constant current charge stage: under the room temperature, carrying out constant current charge with said battery with the electric current of 0.01C, is 4.0V until voltage.
Step b, constant-current discharge stage: shelve, to discharge into voltage be 3.0V to 0.2C then.
After changing into end, the battery performance parameter of test implementation example 5, embodiment 6 and Comparative Examples 3, test result is referring to table 3.Disassemble the battery after embodiment 5, embodiment 6 and Comparative Examples 3 change into, control cell core thickness changes into the back to be changed, and the state of checking cathode pole piece.The technology that wherein adopts embodiment 5 and embodiment 6 to provide changes into battery, and cathode pole piece is only micro-wrinkling.And adopting the prior standard chemical synthesis technology to change into battery, battery changes into back cathode pole piece fracture, and is obviously wrinkling.
Table 2:
Data by table 3 can be known: the technology that adopts embodiment 5 and embodiment 6 to provide changes into battery, and battery changes into back thickness to be increased less than Comparative Examples 3, and cathode pole piece is only micro-wrinkling, and anode pole piece is fracture not; And adopt the prior standard chemical synthesis technology to change into battery, and battery changes into back thickness to be increased above 6%, and cathode pole piece obviously ftractures, and is seriously wrinkling, and anode pole piece obviously ruptures.
Should be understood that; More than be merely the preferred embodiments of the present invention; Can not therefore limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes specification of the present invention and accompanying drawing content to be done, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (6)
1. a lithium ion battery is characterized in that, under-20 ~ 60oC environment, changes into through following steps:
Step 1, the lithium ion battery after fluid injection soaked into carry out the pulse constant current charging, reach designated value until voltage, and the designated value scope of said voltage is 3.4-4.2V;
Step 2, lithium ion battery is carried out constant voltage charge, reach designated value until electric current, the designated value of said electric current is 0.05C;
Step 3, lithium ion battery is carried out constant-current discharge, discharge voltage value scope is 3.0-2.0V, and discharge current value is 0.01-2.0C.
2. lithium ion battery according to claim 1 is characterized in that, following steps are carried out in the circulation that is specially of in the said step 1 lithium ion battery being carried out pulse constant current charging:
Lithium ion battery is carried out constant current charge T with current value I
1Carry out constant current charge T with current value I+△ I again
2Repeat successively, reach designated value up to charging voltage, the designated value scope of said voltage is 3.4-4.2V; Said current value I scope is 0.01-1.0C, and said △ I scope is 0.05-5.0 C, said T
1Scope is 100ms-3600s; Said T
2Be 100 μ s-10s.
3. lithium ion battery according to claim 1 and 2 is characterized in that, the negative active core-shell material of said lithium ion battery is a Si-C composite material, and this Si-C composite material is by carbon phase material and the silicon composite material formed of material mutually.
4. lithium ion battery according to claim 3 is characterized in that, said carbon phase material comprises: any one or more than one mixing in indefinite form carbon, graphite, hard carbon, soft carbon, carbonaceous mesophase spherules, Graphene, CNT, the carbon fiber; Said silicon phase material comprises: elemental silicon, Si oxide (SiO
x), any one or more than one mixing in siliceous solid solution or the silicon intermetallic compound.
5. lithium ion battery according to claim 1 is characterized in that, in the said step 1 lithium ion battery is carried out being specially of pulse constant current charging:
Lithium ion battery is carried out constant current charge T with current value I
1Carry out constant current charge T with current value I+△ I again
2Carry out constant current charge T with current value I then
1Again with current value I+△ I-I
0Carry out constant current charge T
2And the like, the n subpulse begins lithium ion battery is carried out constant current charge T with current value I
1, again with current value I+△ I-(n-1) I
0Carry out constant current charge T
2, as I+ △ I-(n-1) I
0During≤I, then carry out constant current charge with current value I, reach designated value until charging voltage, said designated value scope is 3.4-4.2V; Said current value I scope is 0.01-0.2C, and said △ I scope is 0.05-5.0C, said I
0Scope is 0.0-0.5C; Said T
1Scope is 100ms-3600s, said T
2Be 100 μ s-10s.
6. lithium ion battery according to claim 1 is characterized in that, in the said step 2 lithium ion battery is carried out constant voltage charge and reaches designated value until charging current; Wherein the constant voltage value is a voltage designated value in the step 1, and scope is 3.4-4.2V.
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