CN101685883A - Polymer lithium ion battery and preparation method thereof - Google Patents
Polymer lithium ion battery and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 7
- 229910013716 LiNi Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 19
- 239000010941 cobalt Substances 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002033 PVDF binder Substances 0.000 abstract 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract 5
- 239000007767 bonding agent Substances 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 abstract 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 34
- 230000004087 circulation Effects 0.000 description 19
- 230000035939 shock Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000006183 anode active material Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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)
- Secondary Cells (AREA)
Abstract
The invention discloses a polymer lithium ion battery and preparation method thereof. The method includes the following steps: a) preparing anode plate, lithium nickel, cobalt and manganate, conductive agent and bonding agent are dissolved into anode solvent to obtain anode size, and the anode size is coated on anode current collector; b) preparing cathode plate, graphite, conductive agent, bonding agent and tackify additive are dissolved into cathode solvent to obtain cathode size, and the cathode size is coated on cathode current collector; c) preparing DMC solution of PVDF, polyvinylidene fluoride (PVDF) is dissolved into dimethyl carbonate (DMC), so as to obtain DMC solution of PVDF; d) the anode plate and/or cathode plate are/is placed into PVDF solution; e) the anode plate and the cathode plate are baked and hot-pressed and then assembled with prepared diaphragm, and prepared lithium salt electrolyte is injected. The invention can obviously improve electrochemical performance ofbattery, improve cycling conservation rate of battery, ensures security performance of battery and reduces manufacturing cost of battery.
Description
Technical field
The present invention relates to lithium ion battery and make the field, specifically relate to a kind of preparation method and battery of polymer Li-ion battery.
Background technology
The essential structure of lithium ion battery comprises positive pole, negative pole and three key elements of electrolyte.General lithium-ion technology is used liquid or inorganic colloid electrolyte, therefore needs firm shell to hold active component, and weight and cost that this has just increased battery have also limited the flexibility of battery size size and moulding.As the liquid lithium ionic cell 18650 and 103450 that generally adopts in the market, as Notebook Battery, though in the world it is all had higher requirement at aspects such as safety, storage, circulations, but because the defective of liquid electrolyte itself makes it have bigger hidden danger aspect fail safe, and production cost is higher, quality is heavier, and the trend that this and notebook computer lightness develop is runed counter to.
Poly-lithium battery is meant that the material that has in positive pole, negative pole or the electrolyte more than or has used the lithium ion battery of polymerizable material.Polymer Li-ion battery is the new green environment protection lithium ion battery, has advantages such as thinner, lighter, safer, high power capacity, high discharge platform, long circulation life, heavy-current discharge, small resistor and good cryogenic property and low thermal expansion.In addition, the polymer Notebook Battery adopts a kind of thickness only to pack for the plastic-aluminum packaging film about 0.1mm, has well solved the personalized question of notebook computer design thickness.At present, polymer Li-ion battery is existing preliminary application on notebook computer, and along with constantly widening of its application and updating of technology, its production cost also can decrease, and the polymer Notebook Battery will develop rapidly.
Existingly realized commercialization as the secondary cell of positive electrode with cobalt acid lithium, but owing to the cobalt resource shortage, on the high sidely, poisonous limit it and promote the use of.By contrast, ternary material has advantages such as low cost, high power capacity, high cyclicity, high security, Stability Analysis of Structures.Therefore, adopt ternary material to make polymer battery, then realized the doulbe-sides' victory of battery price and performance, have good DEVELOPMENT PROSPECT as cell positive material.
Summary of the invention
Purpose of the present invention proposes a kind of polymer Li-ion battery and preparation method thereof exactly, the anodal nickle cobalt lithium manganate ternary material that adopts, and the battery of made has high security and high electrochemical performance.
For achieving the above object, the present invention has adopted following technical scheme.
The preparation method of this polymer Li-ion battery may further comprise the steps: a) preparation positive plate, to be dissolved in as nickle cobalt lithium manganate, conductive agent, the adhesive of positive electrode active materials in the anodal solvent, make anode sizing agent, anode sizing agent is coated on the plus plate current-collecting body, make positive plate; B) the preparation negative plate will be dissolved in the negative pole solvent as graphite, conductive agent, adhesive, the adhesion promoting additive (CMC) of negative active core-shell material, makes cathode size, and cathode size is coated on the negative current collector, makes negative plate; The DMC solution of preparation PVDF is dissolved in Kynoar (PVDF) in the dimethyl carbonate (DMC), makes PVDF solution; D) positive plate and/or negative plate being put into PVDF solution soaks; E) to positive and negative plate toast, after the hot pressing with the barrier film assembling of getting ready, inject the lithium salt electrolyte of getting ready.
Among the preparation method of above-mentioned polymer Li-ion battery, the molecular formula of described nickle cobalt lithium manganate is LiNi
N1Co
N2Mn
N3O
2, n1=1/5～2/5 wherein, n2=1/5～2/5, n3=1/5～2/5.
The preparation method of above-mentioned polymer Li-ion battery, in the step a), described anodal solvent is N-methyl pyrrolidone (NMP), the mass ratio of described nickle cobalt lithium manganate, conductive agent, adhesive, N-methyl pyrrolidone is 100: 2.5～3.5: 4.5～5.5: 40～50, is preferably 100: 3: 5: 50.
In the step b), described negative pole solvent is distilled water or deionized water, the mass ratio of described graphite, conductive agent, adhesive, adhesion promoting additive, distilled water or deionized water is 100: 0.5～1.5: 1～2: 2～4: 100～200, is preferably 100: 1: 1.5: 3: 150.
In the step c), Kynoar (PVDF) is 4.5～5.5 with the mass ratio of dimethyl carbonate (DMC): 98～102, be preferably 5: 100.
Also solution is heated to promote the dissolving of Kynoar (PVDF) in dimethyl carbonate (DMC) in the step c).
Described step c) is carried out in full nitrogen environment.
In the step d), the time of described immersion was greater than 12 hours.
The invention also discloses and adopt the prepared polymer Li-ion battery of above-mentioned preparation method.
The present invention is compared with the prior art the beneficial effect that is had: the present invention adopts the nickle cobalt lithium manganate ternary material as battery anode active material, and its molecular formula is LiNi
1/5～2/5Co
1/5～2/5Mn
1/5～2/5O
2, and the Capacity Ratio of ternary material nickle cobalt lithium manganate is higher, and its specific capacity exceeds more than 30% than the sour lithium of cobalt, with cobalt acid lithium identical bound voltage is arranged, and fail safe is stable, and low price is good with the compatibility of lithium salt electrolyte simultaneously, the cycle performance excellence.In preparation process, adopt electrolyte filling method twice, for the first time pole piece is immersed in the DMC solution of PVDF, be beneficial at first on battery pole piece, form gel, the liquid electrolyte that reinjects makes to form jelly glue polymer battery by the abundant Electolyte-absorptive of gel.Adopt the inventive method can significantly improve the chemical property of battery, improve the circulation conservation rate of battery, guarantee the security performance of battery, and reduce production cost of cells.
Description of drawings
Fig. 1 is the cycle performance of battery test result curve chart among the embodiment 1.
Embodiment
Embodiment 1
Battery anode active material: the nickle cobalt lithium manganate ternary material of selecting for use the Shenzhen City Tianjiao Technology Development Co., Ltd to produce, molecular formula is LiNi
1/5Co
2/5Mn
2/5O
2Its physicochemical property is as follows: D50:4.5～7.0um; Specific area: 1.0～1.5m2/g; Pole piece compacted density: 3.0～3.50g/cm3; 1C capacity performance: 140～150mA/g; 50 circulations keep: 99%.
Negative active core-shell material: select native graphite for use.Its physicochemical property is as follows: D50:16～20um; Specific area: 1.2～1.8m2/g; Pole piece compacted density: 1.5～1.7g/cm3; 1C capacity performance 310～350mA/g.
The preparation process of battery may further comprise the steps.
A) preparation positive plate.Calculate by mass, (select 100 parts of ternary material nickle cobalt lithium manganates, 3 parts of acetylene blacks (selecting the BP2000 of Cabot company for use), 5 parts of Kynoar PVDF for use KF7200 as adhesive as conductive agent as positive electrode active materials, Japan Wu Yu chemistry Co., Ltd) is dissolved in 50 parts the anodal solvent N-methyl pyrrolidone (NMP), makes anode sizing agent.Anode sizing agent is coated on the plus plate current-collecting body aluminium foil, adopts back flow roll formula gap double spread, make positive plate.
B) preparation negative plate.Calculate by mass, 100 parts of native graphites as negative active core-shell material, 1 part of acetylene black as conductive agent (selecting Te Migao graphite and Carbon Co., Ltd's product for use), 1.5 parts of styrene butadiene ribbers as adhesive (SBR), 3 parts are dissolved in 150 parts of negative pole solvent distilled water as adhesion promoting additive carboxymethyl cellulose (CMC), make cathode size, cathode size is coated on the negative current collector Copper Foil, adopt back flow roll formula gap double spread, make negative plate, capacity of negative plates is according to the positive electrode capacity limit calculation.
C) preparation barrier film and electrolyte.Barrier film adopts three layers of composite membrane of PP/PE/PP.Press EMC/DEC/MPC/EC (volume ratio) 1.8～2.2: 0.8～1.2: 6.8～7.2: 3.8～4.2 configuration electrolyte solvents, add electrolyte lithium hexafluoro phosphate (LiPF6) and make electrolyte, wherein the concentration of lithium hexafluoro phosphate in electrolyte is 1.0～1.3mo1/L.
D) the DMC solution of preparation PVDF.(25 ± 3 ℃ of ambient temperatures) is dissolved in Kynoar (PVDF) in the dimethyl carbonate (DMC) in the glove box that is full of nitrogen (N2), makes PVDF solution, and wherein Kynoar (PVDF) is 5: 100 with the ratio of dimethyl carbonate (DMC).Can suitably heat and impel its dissolving, finally make the DMC solution of water white PVDF, and to record solution viscosity be 30～45mPas.Kynoar (PVDF) is selected KYNARFLEX 2801 for use, A Kema (China) Investment Co., Ltd product; Dimethyl carbonate (DMC) is selected Fu Lu (Suzhou) new material Co., Ltd product for use.
E) positive plate that branch is cut and negative plate are put into more than the DMC solution immersion 12h of PVDF.
F) will put into after the positive and negative plate taking-up more than 85 ℃ of baking ovens baking 4h; Reusable heat plate hot pressing electricity core, upper and lower hot plate temperature is 55 ℃, pressure is 0.3Mpa; Pack with aluminum plastic film then and it is carried out top side envelope.In being full of the glove box of nitrogen, inject liquid electrolyte afterwards, and then battery is carried out an envelope.One is honored as a queen places battery under normal temperature (25 ± 3 ℃) condition more than the ageing 24h, again battery is carried out precharge and two envelopes, finally changes into, partial volume promptly makes polymer Li-ion battery.
Make 300 groups according to the method described above with batch battery, carry out following test:
1) internal resistance of cell test.After tested, the internal resistance of cell is 20m Ω～25m Ω, the low internal resistance of performance.
2) heavy-current discharge performance test.Monomer electricity core 2C discharge capacity reaches about 96% of 0.5C discharge capacity, and heavy-current discharge performance is good.
3) over-charging 3C/5V test.
Get 50 batteries, experimental condition and process: at first, battery discharge to 2.75V, is charged to battery with the 3C constant current then, after cell voltage reaches 5V, become constant voltage charge, and it is constant to keep 5V voltage 2 hours by constant current charge.
Test result: the battery no leakage, do not smolder, not on fire, do not explode, the over-charging of battery performance is qualified.
4) 130 ℃ of thermal shock tests.
Get 50 batteries, experiment condition and process: at first, with 1C (3800mA) charging, when electric core terminal voltage reaches 4.2V, change constant voltage charge into, be less than or equal to 0.01C until charging current, stop charging, the longest charging interval is not more than 8h.Then, place free convection or moving air baking oven to heat on battery, oven temperature is warmed up to 130 ± 2 ℃ (282 ± 3.6 °F) with 5 ± 2 ℃ of (9 ± 3.6)/min speed, keeps stopping after 30 minutes.
Test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.
5) cycle performance test.
Get 50 batteries, experimental condition, process: with blue electro-detection cabinet test battery cycle performance, concrete work step is as follows:
(1) the 1C constant-current discharge is to 2.75V;
(2) the 1C constant current charge is to 4.2V;
(3) 4.2V constant voltage charge to electric current ends less than 10mA;
(4) leave standstill 2min;
(5) the 1C constant-current discharge is to 2.75V;
(6) and then from work step (2) begin new circulation, stop until 500 times.Concrete cyclic curve as shown in Figure 1.
Test result: 300 circulation volume conservation rates are that 87.47%, 500 circulation volume conservation rate is 82.88%, and cycle performance of battery is good.
Embodiment 2
Its difference from Example 1 is that in the DMC solution of the PVDF of preparation, Kynoar (PVDF) is 4.5: 102 with the ratio of dimethyl carbonate (DMC), and other steps and prescription are with embodiment 1.
Make the battery of 100 same models as stated above.Get 50 batteries and carry out thermal shock test according to method same among the embodiment 1, test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.Get 50 batteries again and carry out the cycle performance test according to the same method among the embodiment 1, test result: 300 circulation volume conservation rates are that 86.21%, 500 circulation volume conservation rate is 82.62%, and cycle performance of battery is good.
Embodiment 3
Its difference from Example 1 is that in the DMC solution of the PVDF of preparation, Kynoar (PVDF) is 5.5: 98 with the ratio of dimethyl carbonate (DMC), and other steps and prescription are with embodiment 1.
Make the battery of 100 same models as stated above.Get 50 batteries and carry out thermal shock test according to method same among the embodiment 1, test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.Get 50 batteries again and carry out the cycle performance test according to the same method among the embodiment 1, test result: 300 circulation volume conservation rates are that 87.15%, 500 circulation volume conservation rate is 82.59%, and cycle performance of battery is good.
Embodiment 4
Its difference from Example 2 is that in the step a), during the preparation positive plate, the mass ratio of nickle cobalt lithium manganate, conductive agent, adhesive, N-methyl pyrrolidone is 100: 2.5: 4.5: 40.In the step b), during the preparation negative plate, the mass ratio of graphite, conductive agent, adhesive, adhesion promoting additive, distilled water or deionized water is 100: 0.5: 1: 2: 100.Other steps and prescription are with embodiment 2.
Make the battery of 100 same models as stated above.Get 50 batteries and carry out thermal shock test according to method same among the embodiment 1, test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.Get 50 batteries again and carry out the cycle performance test according to the same method among the embodiment 1, test result: 300 circulation volume conservation rates are that 86.98%, 500 circulation volume conservation rate is 82.05%, and cycle performance of battery is good.
Embodiment 5
Its difference from Example 3 is that in the step a), during the preparation positive plate, the mass ratio of nickle cobalt lithium manganate, conductive agent, adhesive, N-methyl pyrrolidone is 100: 3.5: 5.5: 50.In the step b), during the preparation negative plate, the mass ratio of graphite, conductive agent, adhesive, adhesion promoting additive, distilled water or deionized water is 100: 1.5: 2: 4: 200.Other steps and prescription are with embodiment 3.
Make the battery of 100 same models as stated above.Get 50 batteries and carry out thermal shock test according to method same among the embodiment 1, test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.Get 50 batteries again and carry out the cycle performance test according to the same method among the embodiment 1, test result: 300 circulation volume conservation rates are that 87.30%, 500 circulation volume conservation rate is 82.25%, and cycle performance of battery is good.
Embodiment 6
Its difference from Example 2 is, the nickle cobalt lithium manganate ternary material that battery anode active material selects for use the Shenzhen City Tianjiao Technology Development Co., Ltd to produce, and molecular formula is LiNi
2/5Co
1/5Mn
2/5O
2Other steps and prescription are with embodiment 2.
Make the battery of 100 same models as stated above.Get 50 batteries and carry out thermal shock test according to method same among the embodiment 1, test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.Get 50 batteries again and carry out the cycle performance test according to the same method among the embodiment 1, test result: 300 circulation volume conservation rates are that 86.96%, 500 circulation volume conservation rate is 82.35%, and cycle performance of battery is good.
Embodiment 7
Its difference from Example 3 is, the nickle cobalt lithium manganate ternary material that battery anode active material selects for use the Shenzhen City Tianjiao Technology Development Co., Ltd to produce, and molecular formula is LiNi
2/5Co
2/5Mn
1/5O
2Other steps and prescription are with embodiment 3.
Make the battery of 100 same models as stated above.Get 50 batteries and carry out thermal shock test according to method same among the embodiment 1, test result: battery outward appearance no change, on fire, do not explode, the battery thermal shock test is unqualified.Get 50 batteries again and carry out the cycle performance test according to the same method among the embodiment 1, test result: 300 circulation volume conservation rates are that 86.30%, 500 circulation volume conservation rate is 82.45%, and cycle performance of battery is good.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. the preparation method of a polymer Li-ion battery is characterized in that, may further comprise the steps:
A) the preparation positive plate will be dissolved in the anodal solvent as nickle cobalt lithium manganate, conductive agent, the adhesive of positive electrode active materials, makes anode sizing agent, and anode sizing agent is coated on the plus plate current-collecting body, makes positive plate;
B) the preparation negative plate will be dissolved in the negative pole solvent as graphite, conductive agent, adhesive, the adhesion promoting additive of negative active core-shell material, makes cathode size, and cathode size is coated on the negative current collector, makes negative plate;
C) the DMC solution of preparation PVDF is dissolved in Kynoar (PVDF) in the dimethyl carbonate (DMC), makes PVDF solution;
D) the DMC solution of positive plate and/or negative plate being put into PVDF soaks;
E) soak after, to positive and negative plate toast, after the hot pressing with the barrier film assembling of getting ready, inject the lithium salt electrolyte of getting ready.
2. the preparation method of polymer Li-ion battery as claimed in claim 1 is characterized in that: in the step c), described Kynoar (PVDF) is 4.5～5.5 with the mass ratio of dimethyl carbonate (DMC): 98～102.
3. the preparation method of polymer Li-ion battery as claimed in claim 2 is characterized in that: in the step c), described Kynoar (PVDF) is 5: 100 with the mass ratio of dimethyl carbonate (DMC).
4. the preparation method of polymer Li-ion battery as claimed in claim 2, it is characterized in that: the molecular formula of described nickle cobalt lithium manganate is LiNi
1/5～2/5Co
1/5～2/5Mn
1/5～2/5O
2
5. the preparation method of polymer Li-ion battery as claimed in claim 2, it is characterized in that: in the step a), described anodal solvent is N-methyl pyrrolidone (NMP), and the mass ratio of described nickle cobalt lithium manganate, conductive agent, adhesive, N-methyl pyrrolidone is 100: 2.5～3.5: 4.5～5.5: 40～50.
6. the preparation method of polymer Li-ion battery as claimed in claim 2, it is characterized in that: in the step b), described negative pole solvent is distilled water or deionized water, and the mass ratio of described graphite, conductive agent, adhesive, adhesion promoting additive, distilled water or deionized water is 100: 0.5～105: 1～2: 2～4: 100～200.
7. the preparation method of polymer Li-ion battery as claimed in claim 6 is characterized in that: also solution is heated to promote the dissolving of Kynoar (PVDF) in dimethyl carbonate (DMC) in the step c).
8. the preparation method of polymer Li-ion battery as claimed in claim 7 is characterized in that: described step c) is being carried out in full nitrogen environment.
9. the preparation method of polymer Li-ion battery as claimed in claim 8, it is characterized in that: in the step d), the time of described immersion was greater than 12 hours.
10. adopt the prepared polymer Li-ion battery of preparation method of any one polymer Li-ion battery in the claim 1 to 9.
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