CN102148405A - Method for manufacturing low-temperature lithium-ion battery - Google Patents
Method for manufacturing low-temperature lithium-ion battery Download PDFInfo
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- CN102148405A CN102148405A CN2011100537111A CN201110053711A CN102148405A CN 102148405 A CN102148405 A CN 102148405A CN 2011100537111 A CN2011100537111 A CN 2011100537111A CN 201110053711 A CN201110053711 A CN 201110053711A CN 102148405 A CN102148405 A CN 102148405A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000003466 welding Methods 0.000 claims abstract description 9
- 239000002985 plastic film Substances 0.000 claims abstract description 6
- 229920006255 plastic film Polymers 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000004513 sizing Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethyl difluoro, methyl Chemical group 0.000 claims description 4
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical group COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 229910012820 LiCoO Inorganic materials 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract 2
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 230000032683 aging Effects 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000007792 addition Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for manufacturing a low-temperature lithium-ion battery, which comprises the following steps of: manufacturing anode paste, manufacturing cathode paste, coating, manufacturing a battery cell, welding tabs, packaging through an aluminum-plastic film, roasting, injecting liquid, exhausting air and sealing an opening, performing formation, ageing, exhausting air and sealing the opening again, and detecting to obtain the battery. In the method, LiCoO2 with the grain size of less than or equal to 10 mu m is adopted, CNTs (carbon nano conductive liquid) is adopted at the anode, an additive with high and low temperature performance is added into a non-water electrolyte, the density of anode dressing and the compacted density of the positive and negative tabs are adjusted, the low-temperature discharge performance of the battery is improved, the high-temperature storage performance of the battery is improved, the lithium-ion battery manufactured by the method can normally work at the ultralow temperature of 40 DEG C below zero, and no gas is generated after the battery is stored at the temperature of 70 DEG C for over 48 hours.
Description
Technical field
The present invention relates to a kind of low-temperature lithium ion battery manufacture method, be specifically related to the method for the lithium ion battery of working under a kind of being manufactured on-40 ℃ condition, this lithium ion battery is storing more than the 48h not aerogenesis under 70 ℃ of conditions.
Background technology
Lithium ion battery has operating voltage height, specific energy height, discharges and recharges life-span length, environmental protection, self-discharge rate is low and advantage such as memory-less effect, at global secondary cell market dominate, range of application more and more widely comprises portable electric appts, communication apparatus, energy storage device, and the power source of relevant walking-replacing tool.To battery electrical property, reliability, the higher occasion of security requirement, such as Aeronautics and Astronautics and military field, lithium-ions battery also will become a star gradually at those.But the cryogenic property of present lithium-ions battery, particularly the service behaviour in low temperature environment below-40 ℃ is relatively poor, has suppressed its application at special dimension.
The lithium ion battery poor performance at low temperatures has following several respects reason: at first, electrolyte is the important component part of lithium ion battery, undertakes the effect of transmitting ion between the inside battery positive and negative electrode, the general non-aqueous organic solvent mixture that is dissolved with lithium salts that adopts.Ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) etc. are present several organic solvents that are widely used in the lithium-ion battery electrolytes.The reduction of the conductivity of electrolyte component is one of reason that causes lithium ion battery cryogenic discharging characteristic difference under cryogenic conditions.Second, under the cryogenic conditions, it also is the reason that causes lithium ion battery low temperature performance difference that lithium ion solid-state diffusion coefficient in electrode reduces, under cryogenic conditions, because the solid-state diffusion coefficient of lithium ion in electrode reduces, the battery discharge platform reduces, and voltage reaches final discharging voltage too early in the guiding discharge process, thereby has reduced discharge capacity of the cell.The 3rd, under the cryogenic conditions, the battery electrochemical impedance increases, and also is the reason that causes the lithium ion battery poor performance at low temperatures.So-called electrochemical impedance is meant, the complexity that electric charge transmits at the electrode/electrolyte interface.The 4th, the structural design mode of battery, surface density size, compacted density size also have certain influence to the low temperature performance of battery.
In order to improve the lithium ion battery low temperature performance, Chinese patent 200410093963.7, CN101017918, E.Jplichta (J.Power Sources, Vol.88, pl192-196,2000) etc. from positive electrode, conductive agent, the low temperature performance of lithium ion battery has been studied in three aspects such as electrolyte, but it all has one-sidedness, simple consideration battery cryogenic property, do not consider the high-temperature behavior of battery, make low-temperature lithium ion battery be restricted in specific use occasion, particularly guaranteeing to take into account high-temperature storage or discharge performance simultaneously under the superior condition of cryogenic property.
Summary of the invention
For solving above technical problem, the present invention mainly provides a kind of manufacture method of high and low temperature lithium ion battery, this lithium ion battery can be under-40 ℃ of condition of ultralow temperature operate as normal, and storing more than the 48h not aerogenesis under 70 ℃ of conditions.
The present invention seeks to realize like this:
(1) preparation of anode sizing agent: the dry powder with anode sizing agent is total weight, joins and gets 87 ~ 95 parts LiCoO
2, 3 ~ 8 parts anodal conductive agent CNTs(carbon conductive nano liquid), anodal binding agent PVDF(Kynoar-hexafluoropropylene of 2 ~ 5 parts), earlier PVDF and solvent NMP are stirred, again CNTs is added stir, at last LiCoO
2Adding stirs, and obtains anode sizing agent, and wherein the CNTs mass concentration is about 3%, and the carbon nano-tube footpath is between 50 ~ 80nm, and pipe range is between 10 ~ 20 μ m, and specific area is greater than 50m
2/ g; It is characterized in that in the anode sizing agent process that CNTs(carbon conductive nano liquid) after disperseing by common process for dispersing, anode sizing agent has characteristics such as collocation method is simple, good uniformity.Whole anode sizing agent good dispersion.
(2) preparation of cathode size: the dry powder with cathode size is total weight, join the negative electrode active material of getting 90 ~ 95 parts, 3 ~ 6 parts cathode conductive agent, 2 ~ 5 parts negative pole binding agent, 1 ~ 2.5 part thickener, mixing is added to the water obtains cathode size through vacuum stirring;
(3) coating: the positive pole slurry that will configure is coated on the aluminium foil of 15～40 μ m, makes positive plate after the oven dry; The negative pole slurry that configures is coated on the electrolytic copper foil, makes negative plate after the oven dry;
(4) preparation of battery: with the coated positive and negative plate of step (3), carry out the roll-in compacting, it is folded mutually to interlock by cross cutting, oven dry, positive and negative plate, forms battery;
(6) lug welding: aluminium, copper nickel plating lug are welded together to form positive and negative lug with positive and negative plate respectively, again through aluminum plastic film encapsulation, baking, fluid injection, bleed seal, change into, wear out, secondary pumping seals, detect and obtain battery, wherein the nonaqueous electrolyte that injects of fluid injection is wherein one or more of organic solvent ethene carbonic ether, propylene carbonate, carbonic acid diethyl ester, dimethyl carbonate, methyl ethyl carbonate fat, and electrolyte lithium salt is LiPF
6, adding mass content in the nonaqueous electrolyte is the additive of this nonaqueous electrolyte 1～5%, this additive is difluoroacetic acid methyl esters, ethyl difluoro, methyl 2,2, one or both in the 2-trifluoroethyl carbonic ether.Not only cryogenic property is good to use the lithium ion battery that this additive makes, and has good high-temperature behavior.
LiCoO in the above-mentioned steps (1)
2≤ 10 μ m.
Negative electrode active material is that graphite, cathode conductive agent are sp(superconduct carbon blacks in the above-mentioned steps (2)), the negative pole binding agent is the SBR(SBR emulsion), thickener is the CMC(sodium carboxymethylcellulose).
Capacity of negative plates/positive electrode capacity is between 1.05 ~ 1.15 in the above-mentioned battery.
Anodal dry powder of anode sizing agent and NMP mass ratio are 6.5:3.5 in the above-mentioned steps (1).
The mass ratio of cathode size negative pole dry powder and water is 3.5:6.5 in the above-mentioned steps (2).
Institute's coating density is 3.5 ~ 3.8g/cm after the middle positive plate roll-in compacting of above-mentioned steps (4)
3Institute's coating density is 1.4 ~ 1.6g/cm after the negative plate roll-in compacting
3
Above-mentioned aluminium, copper nickel plating lug are welded together to form in the process of positive and negative lug with positive and negative plate respectively, and it is two sections that one of them positive and negative plate that welding is good is cut, and links together with two nickel straps between two sections.Battery in use, when battery when meeting with heavy-current discharge or abuse, nickel strap can disconnect, and disconnects institute and connects being connected of lug and battery body, makes battery can not form the formation loop, thereby reaches the protection battery, the purpose of raising battery safety in utilization.
Beneficial effect: the present invention mainly is by adopting the LiCoO of particle diameter≤10 μ m
2The anodal CNTs(carbon conductive nano liquid that adopts), in nonaqueous electrolyte, add the additive that high temperature performance is taken into account, adjust anode dressing density, positive and negative plate compacted density, improve the low temperature performance of battery, improve the high-temperature storage performance of battery, adopt lithium ion battery that above method makes can be under-40 ℃ of condition of ultralow temperature operate as normal, and storing more than the 48h not aerogenesis under 70 ℃ of conditions.
Embodiment
Embodiment 1
Embodiment 1:
(1) preparation of anode sizing agent: the dry powder with anode sizing agent is the total weight umber, join the cobalt acid lithium (particle diameter 7 μ m) of getting 95 parts, 3.0 parts anodal conductive agent CNTs(carbon conductive nano liquid), anodal binding agent PVDF(Kynoar-hexafluoropropylene of 2.0 parts), earlier PVDF and solvent NMP are stirred, again CNTs(conductive nano liquid) add stir, at last LiCoO
2Adding stirs, and obtains anode sizing agent, and anodal dry powder of anode sizing agent and NMP mass ratio are 6.5:3.5 in the preparation;
(2) preparation of cathode size: the dry powder with cathode size is total weight, join the negative electrode active material of getting 92.5 parts, 3 parts cathode conductive agent, 2.0 parts negative pole binding agent, 2.5 parts thickener, be added to the water together and obtain cathode size through vacuum stirring, the mass ratio of negative pole dry powder and water is 3.5:6.5 in the preparation;
(3) coating: the positive pole slurry that will configure is coated on the aluminium foil of 15 μ m, makes positive plate after the oven dry; The cathode size that configures is coated on the electrolytic copper foil, guarantees that the negative pole excess coefficient is 1.15, makes negative plate after the oven dry;
In the coating process, positive pole is coated with 360/m respectively
2(A), 300g/m
2(B), 240g/m
2(C) three kinds of surface densities.
(4) preparation of battery: with the coated positive and negative plate of step (3), carry out the roll-in compacting, it is folded mutually to interlock by cross cutting, oven dry, positive and negative plate, forms battery.
Wherein behind the compressing tablet, anodal bulk density is: 3.6g/cm
3, the negative pole bulk density is 1.4g/cm
3
(6) lug welding: aluminium, copper nickel plating lug are welded together to form positive and negative lug with positive and negative plate respectively, above-mentioned aluminium, copper nickel plating lug are welded together to form in the process of positive and negative lug with positive and negative plate respectively, it is two sections that one of them positive and negative plate that welding is good is cut, and links together with two nickel straps between two sections.Again through aluminum plastic film encapsulation, baking, fluid injection, bleed seal, change into, wear out, secondary pumping seals, detect and obtain battery.The nonaqueous electrolyte that fluid injection is injected is wherein one or more of organic solvent ethene carbonic ether, propylene carbonate, carbonic acid diethyl ester, dimethyl carbonate, methyl ethyl carbonate fat, and electrolyte lithium salt is LiPF
6, adding mass content in the nonaqueous electrolyte is the additive of this nonaqueous electrolyte 1～5%, this additive is difluoroacetic acid methyl esters, ethyl difluoro, methyl 2,2, one or both in the 2-trifluoroethyl carbonic ether.
Test cell is full of electricity after detecting under 25 ℃ of conditions, and 1C discharge under-20 ℃ ,-30 ℃ ,-40 ℃ conditions respectively, and discharge data sees Table 1
Table 1
From the result of table 1 as can be seen, under same cryogenic conditions, along with the increase of surface density, the low temperature discharge ability worse and worse, and category-A can only emit 32% of rated capacity in the time of-40 ℃, and the C class is discharged ratio still more than 85% in the time of-40 ℃;
Embodiment 2:
(1) preparation of anode sizing agent: carry out anode sizing agent according to following different conductive agent additions and join
System earlier stirs PVDF and solvent NMP in the process for preparation, again CNTs(conductive nano liquid) add stir, at last LiCoO
2, LiCoO
2(particle diameter 10 μ m) adding stirs, and obtains anode sizing agent; Anodal dry powder of anode sizing agent and NMP mass ratio are 6.5:3.5 in the preparation;
The positive active material proportioning is as follows:
A LiCoO
2:?CNTs：PVDF=95.5:2:2.5
B LiCoO
2:?CNTs：PVDF=95:4:2.5
C LiCoO
2:?CNTs：PVDF=91.5:6:2.5
D LiCoO
2:?CNTs：PVDF=89.5:8:2.5
(2) preparation of cathode size: the dry powder with cathode size is total weight, join the negative electrode active material of getting 92.5 parts, 3 parts cathode conductive agent, 2.5 parts negative pole binding agent, 2.0 parts thickener, be added to the water together again and obtain cathode size through vacuum stirring; The mass ratio of negative pole dry powder and water is 3.5:6.5 in the preparation;
(3) coating: the positive pole slurry that will configure is coated on the aluminium foil of 20 μ m anodal surface density 300g/m
2, make positive plate after the oven dry; The negative pole slurry that configures is coated on the electrolytic copper foil, guarantees that the negative pole excess coefficient is 1.15, makes negative plate after the oven dry;
(4) preparation of battery: with the coated positive and negative plate of step (3), carry out the roll-in compacting, it is folded mutually to interlock by cross cutting, oven dry, positive and negative plate, forms battery.
Wherein behind the compressing tablet, anodal bulk density is: 3.6g/cm
3, the negative pole bulk density is 1.4g/cm
3
(6) lug welding: aluminium, copper nickel plating lug are welded together to form positive and negative lug with positive and negative plate respectively, again through aluminum plastic film encapsulation, baking, fluid injection, bleed seal, change into, wear out, secondary pumping seals, detect and obtain battery.The nonaqueous electrolyte that fluid injection is injected is wherein one or more of organic solvent ethene carbonic ether, propylene carbonate, carbonic acid diethyl ester, dimethyl carbonate, methyl ethyl carbonate fat, and electrolyte lithium salt is LiPF
6, adding mass content in the nonaqueous electrolyte is the additive of this nonaqueous electrolyte 1～5%, this additive is difluoroacetic acid methyl esters, ethyl difluoro, methyl 2,2, one or both in the 2-trifluoroethyl carbonic ether.
Test cell is full of electricity after detecting under 25 ℃ of conditions, and 1C discharge under-20 ℃ ,-30 ℃ ,-40 ℃ conditions respectively, and discharge data sees Table 2
Table 2
From the result of table 2 as can be seen, under same cryogenic conditions, the low temperature properties discharge performance of battery increases along with the increase of conductive agent content, and when conductive agent content surpassed when being 6% (C class), the low temperature performance of battery tended to be steady.
Embodiment 3:
(1) preparation of anode sizing agent: the dry powder with anode sizing agent is the total weight umber, join the cobalt acid lithium (particle diameter 7 μ m) of getting 93 parts, 3.5 parts anodal conductive agent CNTs(carbon conductive nano liquid), anodal binding agent PVDF(Kynoar-hexafluoropropylene of 2.5 parts), earlier PVDF and solvent NMP are stirred, again CNTs(conductive nano liquid) mass concentration is 3%, add stir, at last LiCoO
2Adding stirs, and obtains anode sizing agent; The CNTs mass concentration is 3%, and the carbon nano-tube footpath is between 50 ~ 80nm, and pipe range is between 10 ~ 20 μ m, and specific area is greater than 50m
2/ g; Anodal dry powder of anode sizing agent and NMP mass ratio are 6.5:3.5 in the preparation;
(2) preparation of cathode size: the dry powder with cathode size is total weight, joins the negative electrode active material of getting 90 parts, 6 parts cathode conductive agent, 5 parts negative pole binding agent, 1 part thickener, is added to the water together and obtains cathode size through vacuum stirring; The mass ratio of negative pole dry powder and water is 3.5:6.5 in the preparation;
(3) coating: the positive pole slurry that will configure is coated on the aluminium foil of 40 μ m, guarantees that its surface density is at 300g/m
2, make positive plate after the oven dry; The negative pole slurry that configures is coated on the electrolytic copper foil, guarantees that the negative pole excess coefficient is 1.05, makes negative plate after the oven dry;
(4) preparation of battery: with the coated positive and negative plate of step (3), carry out the roll-in compacting, it is folded mutually to interlock by cross cutting, oven dry, positive and negative plate, forms battery.
Wherein behind the compressing tablet, anodal bulk density is: 3.6g/cm
3, the negative pole bulk density is 1.4g/cm
3
(6) lug welding: aluminium, copper nickel plating lug are welded together to form positive and negative lug with positive and negative plate respectively, again through aluminum plastic film encapsulation, baking, fluid injection, bleed seal, change into, wear out, secondary pumping seals, detect and obtain battery.
Carry out fluid injection by following different additive amount electrolyte respectively during fluid injection
A EC: DEC: EMC=1:1:1.3, the additive addition: the 0%(mass fraction), LiPF
6Concentration:
1mol/L
B EC: DEC: EMC=1:1:1.3, the additive addition: the 1%(mass fraction), LiPF
6Concentration: 1mol/L
C EC: DEC: EMC=1:1:1.3, the additive addition: the 2%(mass fraction), LiPF
6Concentration: 1mol/L
D EC: DEC: EMC=1:1:1.3, the additive addition: the 3%(mass fraction), LiPF
6Concentration: 1mol/L
E EC: DEC: EMC=1:1:1.3, the additive addition: the 5%(mass fraction), LiPF
6Concentration: 1mol/L
Test cell is full of electricity after detecting under 25 ℃ of conditions, and 1C discharge under-20 ℃ ,-30 ℃ ,-40 ℃ conditions respectively, and discharge data sees Table 3
Table 3
From the result of table 3 as can be seen, along with the increase of electrolysis additive amount, the low temperature performance of battery improves gradually, and the low temperature performance that surpasses 3% battery when additive level descends.When the electrolysis additive amount surpasses 2%, shelve no longer aerogenesis of 48h under 70 ℃ of conditions of battery.
Below only listed anodal use LiCoO
2The result, but in experiment according to above improvement direction, other positive electrodes such as LiMn to cryogenic property
2O
4, LiNi
0.4Co
0.4Mn
0.4O
2Also show same trend.
Battery of the present invention can be made into square flexible package, square box hat, shell with square aluminum, cylindrical battery etc.
Claims (8)
1. the manufacture method of a low-temperature lithium ion battery, carry out as follows:
(1) preparation of anode sizing agent: the dry powder with anode sizing agent is total weight, joins and gets 87 ~ 95 parts LiCoO
2, 3 ~ 8 parts anodal conductive agent CNTs, 2 ~ 5 parts anodal binding agent PVDF, earlier PVDF and solvent NMP are stirred, again CNTs is added stir, at last LiCoO
2Adding stirs, and obtains anode sizing agent, and wherein the CNTs mass concentration is 3%, and the carbon nano-tube footpath is between 50 ~ 80nm, and pipe range is between 10 ~ 20 μ m, and specific area is greater than 50m
2/ g;
(2) preparation of cathode size: the dry powder with cathode size is total weight, join the negative electrode active material of getting 90 ~ 95 parts, 3 ~ 6 parts cathode conductive agent, 2 ~ 5 parts negative pole binding agent, 1 ~ 2.5 part thickener, mixing is added to the water obtains cathode size through vacuum stirring;
(3) coating: the positive pole slurry that will configure is coated on the aluminium foil of 15～40 μ m, makes positive plate after the oven dry; The negative pole slurry that configures is coated on the electrolytic copper foil, makes negative plate after the oven dry;
(4) preparation of battery: with the coated positive and negative plate of step (3), carry out the roll-in compacting, it is folded mutually to interlock by cross cutting, oven dry, positive and negative plate, forms battery;
(6) lug welding: aluminium, copper nickel plating lug are welded together to form positive and negative lug with positive and negative plate respectively, again through aluminum plastic film encapsulation, baking, fluid injection, bleed seal, change into, wear out, secondary pumping seals, detect and obtain battery, wherein the nonaqueous electrolyte that injects of fluid injection is wherein one or more of organic solvent ethene carbonic ether, propylene carbonate, carbonic acid diethyl ester, dimethyl carbonate, methyl ethyl carbonate fat, and electrolyte lithium salt is LiPF
6, adding mass content in the nonaqueous electrolyte is the additive of this nonaqueous electrolyte 1～5%, this additive is difluoroacetic acid methyl esters, ethyl difluoro, methyl 2,2, one or both in the 2-trifluoroethyl carbonic ether.
2. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: LiCoO in the described step (1)
2≤ 10 μ m.
3. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: negative electrode active material is that graphite, cathode conductive agent are that sp, negative pole binding agent are that SBR, thickener are CMC in the described step (2).
4. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: capacity of negative plates/positive electrode capacity is between 1.05 ~ 1.15 in the described battery.
5. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: anodal dry powder of anode sizing agent and NMP mass ratio are 6.5:3.5 in the described step (1).
6. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: the mass ratio of cathode size negative pole dry powder and water is 3.5:6.5 in the described step (2).
7. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: institute's coating density is 3.5 ~ 3.8g/cm after the middle positive plate roll-in compacting of described step (4)
3Institute's coating density is 1.4 ~ 1.6g/cm after the negative plate roll-in compacting
3
8. according to the manufacture method of the described a kind of low-temperature lithium ion battery of claim 1, it is characterized in that: aluminium, copper nickel plating lug are welded together to form in the process of positive and negative lug with positive and negative plate respectively in the described step (6), it is two sections that one of them positive and negative plate that welding is good is cut, and links together with two nickel straps between two sections.
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| CN105261753A (en) * | 2015-08-31 | 2016-01-20 | 无锡市嘉邦电力管道厂 | Water-based cathode slurry for lithium-ion battery and preparation method of water-based cathode slurry |
| CN105552375A (en) * | 2015-12-18 | 2016-05-04 | 山东精工电子科技有限公司 | Carbon nanotube paste for lithium battery and preparation method for carbon nanotube paste |
| CN107742723A (en) * | 2017-08-31 | 2018-02-27 | 新余英泰能科技有限公司 | A kind of preparation method of military super-low-temperature lithium-ion cell |
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| CN111883839A (en) * | 2020-08-03 | 2020-11-03 | 远景动力技术(江苏)有限公司 | High-voltage electrolyte and lithium ion battery based on same |
| CN113517435A (en) * | 2021-06-07 | 2021-10-19 | 江苏劲鹿新能源科技有限公司 | Low-temperature lithium battery formula and sheet-making process |
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Application publication date: 20110810 |