CN102856582A - Square cell of lithium manganate aluminum shell and preparation method - Google Patents
Square cell of lithium manganate aluminum shell and preparation method Download PDFInfo
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- CN102856582A CN102856582A CN2012103827549A CN201210382754A CN102856582A CN 102856582 A CN102856582 A CN 102856582A CN 2012103827549 A CN2012103827549 A CN 2012103827549A CN 201210382754 A CN201210382754 A CN 201210382754A CN 102856582 A CN102856582 A CN 102856582A
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- volume core
- limn2o4
- aluminum hull
- core
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- 238000002360 preparation method Methods 0.000 title claims description 17
- KLXIKSYLRKIVQM-UHFFFAOYSA-N aluminum lithium dioxido(dioxo)manganese Chemical compound [Mn](=O)(=O)([O-])[O-].[Li+].[Al+3].[Mn](=O)(=O)([O-])[O-] KLXIKSYLRKIVQM-UHFFFAOYSA-N 0.000 title abstract 2
- -1 polypropylene Polymers 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000004743 Polypropylene Substances 0.000 claims abstract description 24
- 239000006258 conductive agent Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 229920001155 polypropylene Polymers 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004804 winding Methods 0.000 claims abstract description 7
- 239000005030 aluminium foil Substances 0.000 claims abstract description 6
- 239000011889 copper foil Substances 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 47
- 229910052782 aluminium Inorganic materials 0.000 claims description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 38
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000000084 colloidal system Substances 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 21
- 239000007924 injection Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 238000003466 welding Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007888 film coating Substances 0.000 claims description 4
- 238000009501 film coating Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 15
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910021382 natural graphite Inorganic materials 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000006255 coating slurry Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a square cell of a lithium manganate aluminum shell. The coiled core of the cell comprises a plurality of coiled core units with a same specification. The exteriors of a plurality of coiled core units are camped, arranged and fixed by coiled core auxiliary modules and the coiled core units are arranged in a shell. The coiled core auxiliary modules are made of polypropylene (PP). Aluminium foil is coated with positive pole slurry to form a positive piece and copper foil is coated with negative pole slurry to form a negative piece. The positive pole slurry comprises the components of lithium manganate, conductive agent and binder which are mixed and the negative pole slurry comprises the components of natural graphite, a conductive agent and a binder which are mixed. The square cell has the characteristics that (1) the cylinder winding coiled core is adopted, a gap and the tightness degree of the pole pieces are even and the production efficiency is high; (2) the coiled core auxiliary modules can support and protect the coiled core, and thus the mechanical strength and the safety of the cell are improved; (3) the size of the square cell after grouping can be matched with that of a lead-acid cell with a same volume, particularly the lead-acid cell of an electric bicycle.
Description
Technical field
The invention belongs to the lithium ion battery field, be mainly used in the electrokinetic cell fields such as electric bicycle, electric motor car.Particularly relate to a kind of LiMn2O4 aluminum hull rectangular cell and preparation method.
Background technology
Mainly contain lead-acid battery and lithium ion battery two large classes in the electrokinetic cell field.Lead-acid battery relies on most of market that its low-cost and ripe technique and good security performance have occupied the electrokinetic cell field in the past few decades.But lead-acid battery also has its fatal weakness: energy density is low, cycle performance is poor.The specific discharge capacity of lead-acid battery is only at 30Wh/Kg-50Wh/Kg, and volumetric specific energy is only at 70 Wh/l-100 Wh/l, and cycle life is only about 300 times.And lead-acid battery has pollution to environment, so government put into effect a series of policies in recent years, has improved the threshold trip that enters of lead-acid battery.
Lithium ion battery emerges rapidly with its high voltage, high-energy-density, good cycle performance, the advantage such as environment friendly and pollution-free.The lithium ion battery take LiMn2O4 as positive electrode has particularly obtained increasing application with its high conformity, advantage that cost is low in the electrokinetic cell field.
Lithium-ion-power cell is rectangular cell particularly; the normal operation metal shell plays a protective role to battery core; also play simultaneously the effect of auxiliary fluid injection, but metal shell is subject to metal shell distortion after the external force extruding, the volume core of the inside is had injury to a certain degree and damages battery core.In addition, insert cylindrical roll core back casing in the square casing and volume core gap is larger, be unfavorable for fluid injection, therefore need to take the module of auxiliary fluid injection to solve the fluid injection problem.This is key problems-solving of the present invention just.
Although the lithium ion battery particularly lithium ion battery of manganate cathode material for lithium has series of advantages, but because cost is higher, be difficult to extensive in the short time in the replacement lead-acid battery, this needs an incremental process, if the size of the LiMn2O4 electrokinetic cell that therefore designs is rear size near lead-acid battery in groups, undoubtedly good impetus is played in the popularization of lithium-ion-power cell.
Battery diaphragm refers to one deck diaphragm material between anode and negative pole, it is part very crucial in the battery, battery security and cost are had a direct impact, its Main Function is: the isolation positive and negative electrode also makes the electronics in the battery not pass freely through, and allows the ion in the electrolyte freely pass through between both positive and negative polarity.Battery diaphragm the ionic conduction ability be directly connected to the overall performance of battery; effect of its isolation both positive and negative polarity make battery in the situation that overcharge or temperature raise can Limited Current rising; prevent that battery short circuit from setting off an explosion; have the self-closing protective effect of micropore, battery user and equipment are played the effect of safeguard protection.The conventional barrier film of present used in battery normally adopts polyethylene, polypropylene preparation, exists in actual use the not good easy short circuit of insulation effect, ion to spread defective undesirable and that intensity is relatively poor.
Summary of the invention
The objective of the invention is the problem that exists for prior art, propose a kind of LiMn2O4 aluminum hull rectangular cell and preparation method, mainly solved aluminum-shell battery yielding and damage the problem of battery core; Mainly solved and inserted the problem that electrolyte behind the cylindrical roll core infiltrates battery core in the rectangular cell.
For achieving the above object, the present invention takes following scheme:
A kind of LiMn2O4 aluminum hull rectangular cell comprises aluminium casing, volume core and electrolyte, and wherein, housing is comprised of shell and cover plate two parts, and cover plate is provided with anode collection post, negative pole currect collecting post, explosion-proof valve and insulating trip; The volume core is that positive and negative plate and barrier film stack gradually the cylindrical roll core that is wound into, and the volume core places in the housing, and anode ear, the negative electrode lug of volume core are connected with anode collection post, the negative pole currect collecting post of cover plate by plus plate current-collecting body, negative current collector respectively.The volume core is comprised of the volume core unit of a plurality of same specifications, and a plurality of volume core units outside is arranged by the clamping of volume core supplementary module and fixedly is placed in the housing, and volume core supplementary module is the PP material; Positive plate is to be coated on the aluminium foil with anode sizing agent, and negative plate is to be coated on the Copper Foil by cathode size; Described anode sizing agent is to be mixed by LiMn2O4 and conductive agent, binding agent, and cathode size is to be mixed by native graphite and conductive agent, binding agent.
Described anode sizing agent is to be 87 ~ 91 parts LiMn2O4,4 ~ 6 parts conductive agent, 5 ~ 7 parts binding agent reconcile into solid content 45% ~ 65% with METHYLPYRROLIDONE slurry with weight portion; Described cathode size is to be 89 ~ 93 parts native graphite, 2 ~ 4 parts conductive agent, 5 ~ 7 parts binding agent reconcile into solid content 30% ~ 50% with deionized water slurry with weight portion.
Described conductive agent is conductive black and/or electrically conductive graphite, and described binding agent is the one or more combination of polyvinylidene fluoride or water-base cement, CMC, butadiene-styrene rubber.
Described volume core supplementary module is that two volume core supplementary modules are along the axially rectangle overall structure to being combined into of volume core, its outside and rectangular housing is pegged graft and is cooperated, inside is provided with and the cylindrical groove of rolling up core and pegging graft and to cooperate, two volume core supplementary modules are provided with projection and the groove that mutual grafting cooperates at its involutory surface, and volume core supplementary module is provided with inside and outside through hole or the groove that connects.
Described volume core supplementary module is that two volume core supplementary modules are along the rectangle overall structure of neighboring to being combined into of volume core, its outside and rectangular housing is pegged graft and is cooperated, inside is provided with and the arc groove of rolling up core and pegging graft and to cooperate, two volume core supplementary modules are provided with projection and the groove that mutual grafting cooperates at its involutory surface, and volume core supplementary module is provided with inside and outside through hole or the groove that connects.
Two volume core supplementary modules comprise upper and lower butted structure and left and right butted structure along the involutory mode in neighboring of rolling up core.
Described barrier film composed as follows: take the barrier film of polypropylene, polyethylene material as matrix, the coating that is formed by polymeric colloid material and inorganic filler in the matrix surface coating; The mixture that described polymeric colloid material is comprised of Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile and polymethyl methacrylate; Described inorganic filler is a kind of or its compositions of mixtures by nanometer-level inorganic powder material alundum (Al2O3), silicon dioxide.The barrier film matrix of described polypropylene, polyethylene material is selected polypropylene microporous film or three layers of composite microporous separator of polypropylene, polyethylene/polypropylene; Described inorganic filler granularity is 50nm-200nm; Described barrier film coating layer thickness is 1-5 μ m; Process is coated with the barrier film porosity of polymeric colloid material and inorganic filler processing between 30%-50%; Described barrier film coating layer thickness is preferably 2-3 μ m; The weight of described inorganic filler accounts for the 30%-100% of coated polymeric colloidal materials weight.
Kynoar in the polymeric colloid material, vinylidene fluoride-hexafluoropropylene copolymer account for the 40%-70% of overall polymeric colloid material weight; Polyacrylonitrile accounts for the 5%-20% of overall polymeric colloid material weight; Polymethyl methacrylate accounts for the 10%-40% of overall polymeric colloid material weight.
Polymeric colloid material solvent for use is selected from one or more of following solvent: butanone, acetone, oxolane, 1-METHYLPYRROLIDONE, ethyl acetate, ethanol, diethyl carbonate, butanols.
The preparation method of foregoing LiMn2O4 aluminum hull rectangular cell is characterized in that, may further comprise the steps:
(1) batching: the preparation of anode sizing agent is that conductive agent and LiMn2O4 are toasted first, binding agent is added the METHYLPYRROLIDONE mediation stir, and adds conductive agent and continues to stir, and adds at last the slurry that LiMn2O4 stirs into thickness; The cathode size preparation is the slurry that each raw material is stirred into thickness by proportioning;
(2) coating: the positive pole that will stir and cathode size are coated on aluminium foil and the Copper Foil respectively equably, and the zone that leaves some space, as the lug district;
(3) baking: pole coating is complete to be toasted first afterwards, and the circulation baking forwarded subsequent processing to after 20-26 hour in vacuum oven;
(4) roll-in: positive/negative plate is cut edge first again roll-in to suitable thickness by roll squeezer;
(5) itemize film-making: the pole piece after the roll-in is carried out itemize by banding machine, then weld the lug of pure nickel material or pure aluminum material at blank space;
(6) baking: pole piece is made complete baking 20-26 hour that circulates again, then forwards subsequent processing to;
(7) reel: during assembling, diaphragm clip is stacked between positive/negative plate, be wound on the pin with average tensile force, will roll up the core winding with adhesive tape after the winding and wrap;
(8) assembling: the volume core anode ear that will spool adopts supersonic welder to be welded on the plus plate current-collecting body aluminium strip; Negative pole lug welding is on negative current collector nickel strap or copper strips; Then pack into and roll up core supplementary module and the housing of packing into, adopt Laser Welding or supersonic welding to be connected with the anode collection post of cover plate the plus plate current-collecting body aluminium strip again, adopt Laser Welding or supersonic welding to be connected with the negative pole currect collecting post of cover plate negative current collector nickel strap or copper strips; At last with cover plate and housing seal welding;
(9) fluid injection: in the liquid injection hole of cover plate, carry out fluid injection.
Further comprising the steps of after the fluid injection: (10) change into: must change into by Over-The-Counter in 24 ~ 48 hours after the fluid injection, at first the electric current with 0.02C-0.05C is charged to voltage 3.4V in advance, then the current charges with 0.2C transfers constant voltage charge to 4.2V, termination electric current 0.02C-0.05C.Be discharged to 3.0V with 0.2C again after being full of, the electric current with 0.5C discharges and recharges once again, with the discharge capacity of the 0.5C capacity that changes into as battery.
In preparation cathode size process, when use comprises the binding agent of CMC, first CMC is added deionized water for stirring, add again conductive agent and continue to stir, then add native graphite and stir, add at last other binding agent and stir into slurry.
Positive/negative plate is all taked Double-pole lug.
What the present invention adopted is the coiled volume core unit combination of cylinder, has advantages of cylinder takeup type battery core; Taked volume core supplementary module, strengthened the security performance of battery, the fluid injection that also is conducive to roll up core simultaneously; The one-tenth packet size coupling of this battery is conducive to applying of this battery with the lead-acid battery of capacity.Battery separator of the present invention is gel polymer electrolyte film simultaneously, it adopts take Kynoar, vinylidene fluoride-hexafluoropropylene copolymer electrolyte colloid as matrix, the imbibition ability, the ionic conduction ability that add polyacrylonitrile, polymethyl methacrylate, inorganic nano level powder body material raising colloid, adopting the barrier film of polypropylene, polyethylene material is the matrix of polymeric colloid, has solved polymer dielectric colloid film mechanical strength problem rambunctious.The content that the present invention adjusts Kynoar, vinylidene fluoride-hexafluoropropylene copolymer improves membrane surface polymeric colloid adhesive property and polymer amorphous substance content, adds imbibition ability, the ionic conduction ability of polyacrylonitrile, polymethyl methacrylate, inorganic nano level powder body material raising colloid.To sum up this barrier film has improved the anti-short circuit of battery, anti-acupuncture, shock resistance, anti-extrusion ability, and then improves and improved the security performance of lithium ion battery.
Description of drawings
Fig. 1 is a kind of overall schematic of LiMn2O4 10 ampere-hour aluminum hull rectangular cells.
Fig. 2 is the three-view diagram of volume core supplementary module, and wherein 2a is front view, and 2b is right view, and 2c is upward view.
Fig. 3 is the assembling schematic diagram of volume core and volume core supplementary module.
Embodiment
The below is further detailed the technical scheme in the embodiment of the invention.Obviously; described embodiment only is the present invention's part embodiment, rather than whole embodiment, based on embodiments of the invention; the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work belongs to the scope of protection of the invention.
The invention discloses a kind of LiMn2O4 10 ampere-hour aluminum hull rectangular cells, comprise housing, volume core supplementary module, positive plate, negative plate and electrolyte.Housing is aluminum hull, comprises shell and cover plate; Volume core supplementary module is the PP material, act as (1) auxiliary electrolyte and infiltrates the volume core.(2) support and protect the volume core; Positive plate is to be coated on the aluminium foil by anode sizing agent, and negative plate is to be coated on the Copper Foil by cathode size.Anode sizing agent is to be mixed by lithium manganate material and conductive agent, binding agent.Cathode size is to be mixed by native graphite and conductive agent, binding agent.Positive/negative plate and barrier film stack gradually and are wound into two cylindrical roll cores, then assemble with volume core supplementary module, aluminum hull, and last fluid injection changes into.Cell integrated schematic diagram as shown in Figure 1.
Described a kind of LiMn2O4 10 ampere-hour rectangular cells are of a size of: long 70mm ± 1mm, wide 35mm ± 1mm highly is 73mm ± 1mm.Preferably, the thickness of aluminum hull is 0.25-0.5mm.The 12V10Ah lead-acid battery of 6-DZM-10 model is of a size of at present: 151mm * 99mm * 95mm, for the lead-acid battery group of 36V10Ah, assembled dimension is: 151mm * 99mm * 285mm, and the 10 ampere-hour LiMn2O4 rectangular cells of 10 the present embodiment are of a size of through behind the tandem compound of certain way: 140mm * 73mm * 175mm, therefore can mate the space of placing lead-acid battery, be conducive in the situation that do not change the battery case placement with the lithium manganate battery of capacity.This popularization for lithium ion battery provides favourable condition.
Described volume core supplementary module, structure as shown in Figure 2.Wherein c-1 is projection, and c-2 is groove.C-1 and c-2 play the effect of fixing two volume core supplementary modules.C-3 is a groove, is the passage that plus plate current-collecting body and negative current collector are drawn.C-4 is bar hole, is the passage that electrolyte infiltrates the volume core.Circular holes in the middle of the supplementary module is used for the assembling of cylindrical roll core unit and fixing.Volume core supplementary module plays two effects: (1) auxiliary electrolyte infiltrates the volume core.(2) support and protect the volume core.Preferably, supplementary module is that the PP material adds fire retardant and glass fibre to strengthen security performance and mechanical strength.
Described a kind of LiMn2O4 10 ampere-hour aluminum hull rectangular cells, preferably,
The percentage by weight proportioning of anode sizing agent:
Positive electrode: 87% ~ 91%
Conductive carbon black: 2% ~ 3%
Electrically conductive graphite: 2% ~ 3%
Polyvinylidene fluoride: 5% ~ 7%
Solid content 45% ~ 65%.
The percentage by weight proportioning of cathode size:
Negative material: 89% ~ 93%
Conductive black: 1% ~ 2%
Electrically conductive graphite .1% ~ 2%
CMC: 1% ~ 2%
Butadiene-styrene rubber (amount of solid): 4% ~ 5%
Solid content 30% ~ 50%.
The manufacture craft of described a kind of LiMn2O4 10 ampere-hour aluminum hull rectangular cells, preferred following steps:
(1) batching: preferred following methods:
A. prepare anode sizing agent.Material requested is: polyvinylidene fluoride 5% ~ 7%, LiMn2O4: 87% ~ 91%, conductive carbon black: 2% ~ 3%, electrically conductive graphite: 2% ~ 3%.Solid content 45% ~ 65%.Conductive agent and LiMn2O4 all need toast, and polyvinylidene fluoride is added METHYLPYRROLIDONE stir, and add conductive black and electrically conductive graphite and continue to stir, and add at last the slurry that LiMn2O4 stirs into thickness.
B. prepare cathode size.Material requested is: native graphite 89% ~ 93%; Conductive black 1% ~ 2%; Electrically conductive graphite 1% ~ 2%; CMC 1% ~ 2%; Butadiene-styrene rubber 4% ~ 5%; Solid content 30% ~ 50%.First CMC is added deionized water for stirring, add again conductive black and electrically conductive graphite and continue to stir, then add native graphite and stir, add at last SBR emulsion and stir into slurry.
(2) coating: the negative or positive electrode slurry that stirs is coated on the metal forming collector equably, and the zone that leaves some space, as the tab welding district, then entering the coating machine oven baking, baking namely becomes the both positive and negative polarity pole piece after doing.
(3) baking: pole coating is complete to be toasted first afterwards, and the circulation baking forwarded subsequent processing in 24 hours in vacuum oven.
(4) roll-in: positive/negative plate is cut edge first again roll-in to suitable thickness by roll squeezer.
(5) itemize film-making: the pole piece after the roll-in is carried out itemize by banding machine, then weld the lug of pure nickel material or pure aluminum material at blank space.For the high rate performance that guarantees that battery is good, positive/negative plate is all taked Double-pole lug.
(6) baking: pole piece is made the complete baking 24 hours that circulates again, then forwards subsequent processing to.
(7) reel: during assembling, a pair of positive/negative plate and barrier film are stacked successively, be wound on the pin with suitable and average tensile force, will roll up the core winding with adhesive tape after the winding and wrap.
(8) assembling: two volume core anode ears will spooling adopt supersonic welder to be welded on the specific plus plate current-collecting body aluminium strip; Negative pole lug welding is on specific negative current collector nickel strap or copper strips.Then pack into and roll up core supplementary module and the aluminum hull of packing into, adopt Laser Welding or supersonic welding to be connected with the anode collection post of cover plate the plus plate current-collecting body aluminium strip again, adopt Laser Welding or supersonic welding to be connected with the negative pole currect collecting post of cover plate negative current collector nickel strap or copper strips.At last with cover plate and aluminum hull seal welding.The assembling schematic diagram as shown in Figure 3.
(9) fluid injection: carry out fluid injection in the liquid injection hole of cover plate, reservoir quantity is 38 ± 2g.
(10) change into: must change into by Over-The-Counter in 24 ~ 48 hours after the fluid injection.At first the electric current with 0.02C-0.05C is charged to voltage 3.4V in advance, and then the current charges with 0.2C transfers constant voltage charge to 4.2V, termination electric current 0.02C-0.05C.Be discharged to 3.0V with 0.2C again after being full of, the electric current with 0.5C discharges and recharges once again, with the discharge capacity of the 0.5C capacity that changes into as battery.
(11) partial volume: the battery that the electrical property indices is all met technological requirement is placed respectively the people storehouse.
Several exemplary embodiments of the barrier film preparation that the volume core adopts among the present invention below are provided.
3000g Kynoar, 6000g vinylidene fluoride-hexafluoropropylene copolymer, 800g polyacrylonitrile, 5000g polymethyl methacrylate are dissolved in 50000g acetone, 2000g ethyl acetate, the 1000g alcohol solvent, solution temperature 40-80 ℃, add again the 2500g alundum (Al2O3), 2500g silicon dioxide carries out dispersed with stirring, makes thick slurry.The thick slurry that will prepare with coating device is coated on the polypropylene microporous film, the barrier film of coating slurry is dried in the coating device baking oven, barrier film after the oven dry is through 80 ℃ of vacuum bakeouts, remove residual solvent, just obtain the used barrier film of volume core in the previous embodiment, according to lithium-ion-power cell manufacturer demand, barrier film can be made the different in width barrier film through cutting.
With the 3000g Kynoar, the 3000g vinylidene fluoride-hexafluoropropylene copolymer, the 800g polyacrylonitrile, the 4500g polymethyl methacrylate is dissolved into 15000g acetone, the 15000g oxolane, 2000g ethyl acetate, in the 1000g alcohol solvent, solution temperature 40-80 ℃, add again the 5000g alundum (Al2O3) and carry out dispersed with stirring, make thick slurry, the thick slurry that to make with coating device is coated in polypropylene, on the barrier film of polyethylene material, the barrier film of coating slurry is dried in the coating device baking oven, barrier film after the oven dry is through 80 ℃ of vacuum bakeouts, remove residual solvent, just obtain the used barrier film of volume core in the previous embodiment, according to lithium-ion-power cell manufacturer demand, barrier film can be made the different in width barrier film through cutting.
With the 4000g Kynoar, the 6000g vinylidene fluoride-hexafluoropropylene copolymer, the 800g polyacrylonitrile, the 5000g polymethyl methacrylate is dissolved into the 50000g 1-METHYLPYRROLIDONE, 2000g ethyl acetate, in the 1000g alcohol solvent, solution temperature 40-80 ℃, add again the 6000g alundum (Al2O3) and carry out dispersed with stirring, make thick slurry, the thick slurry that to make with coating device is coated in polypropylene, on the barrier film of polyethylene material, the barrier film of coating slurry is dried in the coating device baking oven, barrier film after the oven dry is through 80 ℃ of vacuum bakeouts, remove residual solvent, just obtain the used barrier film of volume core in the previous embodiment, according to lithium-ion-power cell manufacturer demand, barrier film can be made the different in width barrier film through cutting.
Embodiment 5
With the 4000g Kynoar, the 6000g vinylidene fluoride-hexafluoropropylene copolymer, the 800g polyacrylonitrile, the 5000g polymethyl methacrylate is dissolved into the 25000g butanone, the 25000g oxolane, the 1000g diethyl carbonate, 1000g ethyl acetate, in the 1000g butanols solvent, solution temperature 40-80 ℃, add again the 3500g alundum (Al2O3), 2500g silicon dioxide carries out dispersed with stirring, make thick slurry, the thick slurry that to make with coating device is coated in polypropylene, on the barrier film of polyethylene material, the barrier film of coating slurry is dried in the coating device baking oven, barrier film after the oven dry is through 80 ℃ of vacuum bakeouts, remove residual solvent, just obtain the used barrier film of volume core in the previous embodiment, according to lithium-ion-power cell manufacturer demand, barrier film can be made the different in width barrier film through cutting.
Embodiment 6
With the 5000g Kynoar, the 4000g vinylidene fluoride-hexafluoropropylene copolymer, the 800g polyacrylonitrile, the 5000g polymethyl methacrylate is dissolved into the 25000g butanone, the 25000g oxolane, the 1000g diethyl carbonate, 1000g ethyl acetate, in the 1000g butanols solvent, solution temperature 40-80 ℃, add again 6500g silicon dioxide and carry out dispersed with stirring, make thick slurry, the thick slurry that to make with coating device is coated in polypropylene, on the barrier film of polyethylene material, the barrier film of coating slurry is dried in the coating device baking oven, barrier film after the oven dry is through 80 ℃ of vacuum bakeouts, remove residual solvent, just obtain the used barrier film of volume core in the previous embodiment, according to lithium-ion-power cell manufacturer demand, barrier film can be made the different in width barrier film through cutting.
Embodiment 7
With the 3000g Kynoar, the 6000g vinylidene fluoride-hexafluoropropylene copolymer, the 800g polyacrylonitrile, the 5000g polymethyl methacrylate is dissolved into the 50000g 1-METHYLPYRROLIDONE, the 1000g diethyl carbonate, 1000g ethyl acetate, in the 1000g butanols solvent, solution temperature 40-80 ℃, add again the 7500g alundum (Al2O3) and carry out dispersed with stirring, make thick slurry, the thick slurry that to make with coating device is coated in polypropylene, on the barrier film of polyethylene material, the barrier film of coating slurry is dried in the coating device baking oven, barrier film after the oven dry is through 80 ℃ of vacuum bakeouts, remove residual solvent, just obtain the used barrier film of volume core in the previous embodiment, according to lithium-ion-power cell manufacturer demand, barrier film can be made the different in width barrier film through cutting.
With the lithium ion battery that the method is made, employing be the coiled volume core unit combination of cylinder, have advantages of cylinder takeup type battery core; Taked volume core supplementary module, strengthened the security performance of battery, the fluid injection that also is conducive to roll up core simultaneously; The one-tenth packet size coupling of this battery is conducive to applying of this battery with the lead-acid battery of capacity.
For the above-mentioned explanation of the disclosed embodiments, only be preferred embodiment of the present invention, be not to limit practical range of the present invention.Be that every equivalence of doing according to the content in the present patent application claim changes and modification, all should be technology category of the present invention.
Claims (13)
1. a LiMn2O4 aluminum hull rectangular cell comprises aluminium casing, volume core and electrolyte, and wherein, housing is comprised of shell and cover plate two parts, and cover plate is provided with anode collection post, negative pole currect collecting post, explosion-proof valve and insulating trip; The volume core is that positive and negative plate and barrier film stack gradually the cylindrical roll core that is wound into, the volume core places in the housing, anode ear, the negative electrode lug of volume core are connected with anode collection post, the negative pole currect collecting post of cover plate by plus plate current-collecting body, negative current collector respectively, it is characterized in that: the volume core is that the volume core unit of a plurality of same specifications forms, a plurality of volume core units outside is arranged by the clamping of volume core supplementary module and fixedly is placed in the housing, and volume core supplementary module is the PP material; Positive plate is to be coated on the aluminium foil with anode sizing agent, and negative plate is to be coated on the Copper Foil by cathode size; Described anode sizing agent is to be mixed by LiMn2O4 and conductive agent, binding agent, and cathode size is to be mixed by native graphite and conductive agent, binding agent.
2. LiMn2O4 aluminum hull rectangular cell according to claim 1 is characterized in that: described anode sizing agent is to be 87 ~ 91 parts LiMn2O4,4 ~ 6 parts conductive agent, 5 ~ 7 parts binding agent reconcile into solid content 45% ~ 65% with METHYLPYRROLIDONE slurry with weight portion; Described cathode size is to be 89 ~ 93 parts native graphite, 2 ~ 4 parts conductive agent, 5 ~ 7 parts binding agent reconcile into solid content 30% ~ 50% with deionized water slurry with weight portion.
3. LiMn2O4 aluminum hull rectangular cell according to claim 2, it is characterized in that: described conductive agent is conductive black and/or electrically conductive graphite, and described binding agent is the one or more combination of polyvinylidene fluoride or water-base cement, CMC, butadiene-styrene rubber.
4. according to claim 1 and 2,3 described LiMn2O4 aluminum hull rectangular cells, it is characterized in that: described volume core supplementary module is that two volume core supplementary modules are along the axially rectangle overall structure to being combined into of volume core, its outside and rectangular housing is pegged graft and is cooperated, inside is provided with and the cylindrical groove of rolling up core and pegging graft and to cooperate, two volume core supplementary modules are provided with projection and the groove that mutual grafting cooperates at its involutory surface, and volume core supplementary module is provided with inside and outside through hole or the groove that connects.
5. according to claim 1 and 2,3 described LiMn2O4 aluminum hull rectangular cells, it is characterized in that: described volume core supplementary module is that two volume core supplementary modules are along the rectangle overall structure of neighboring to being combined into of volume core, its outside and rectangular housing is pegged graft and is cooperated, inside is provided with and the arc groove of rolling up core and pegging graft and to cooperate, two volume core supplementary modules are provided with projection and the groove that mutual grafting cooperates at its involutory surface, and volume core supplementary module is provided with inside and outside through hole or the groove that connects.
6. LiMn2O4 aluminum hull rectangular cell according to claim 5 is characterized in that: roll up the core supplementary modules for two and comprise upper and lower butted structure and left and right butted structure along the involutory mode in neighboring of rolling up core.
7. LiMn2O4 aluminum hull rectangular cell according to claim 1 is characterized in that: described barrier film composed as follows: take the barrier film of polypropylene, polyethylene material as matrix, and the coating that is formed by polymeric colloid material and inorganic filler in the matrix surface coating; The mixture that described polymeric colloid material is comprised of Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile and polymethyl methacrylate; Described inorganic filler is a kind of or its compositions of mixtures by nanometer-level inorganic powder material alundum (Al2O3), silicon dioxide; The barrier film matrix of described polypropylene, polyethylene material is selected polypropylene microporous film or three layers of composite microporous separator of polypropylene, polyethylene/polypropylene; Described inorganic filler granularity is 50nm-200nm; Described barrier film coating layer thickness is 1-5 μ m; Process is coated with the barrier film porosity of polymeric colloid material and inorganic filler processing between 30%-50%; Described barrier film coating layer thickness is preferably 2-3 μ m; The weight of described inorganic filler accounts for the 30%-100% of coated polymeric colloidal materials weight.
8. LiMn2O4 aluminum hull rectangular cell according to claim 7, it is characterized in that: the Kynoar in the polymeric colloid material, vinylidene fluoride-hexafluoropropylene copolymer account for the 40%-70% of overall polymeric colloid material weight; Polyacrylonitrile accounts for the 5%-20% of overall polymeric colloid material weight; Polymethyl methacrylate accounts for the 10%-40% of overall polymeric colloid material weight.
9. LiMn2O4 aluminum hull rectangular cell according to claim 8, it is characterized in that: polymeric colloid material solvent for use is selected from one or more of following solvent: butanone, acetone, oxolane, 1-METHYLPYRROLIDONE, ethyl acetate, ethanol, diethyl carbonate, butanols.
10. according to the preparation method of the described LiMn2O4 aluminum hull of the arbitrary claim of 4-9 rectangular cell, it is characterized in that, may further comprise the steps:
(1) batching: the preparation of anode sizing agent is that conductive agent and LiMn2O4 are toasted first, binding agent is added the METHYLPYRROLIDONE mediation stir, and adds conductive agent and continues to stir, and adds at last the slurry that LiMn2O4 stirs into thickness; The cathode size preparation is the slurry that each raw material is stirred into thickness by proportioning;
(2) coating: the positive pole that will stir and cathode size are coated on aluminium foil and the Copper Foil respectively equably, and the zone that leaves some space, as the lug district;
(3) baking: pole coating is complete to be toasted first afterwards, and the circulation baking forwarded subsequent processing to after 20-26 hour in vacuum oven;
(4) roll-in: positive/negative plate is cut edge first again roll-in to suitable thickness by roll squeezer;
(5) itemize film-making: the pole piece after the roll-in is carried out itemize by banding machine, then weld the lug of pure nickel material or pure aluminum material at blank space;
(6) baking: pole piece is made complete baking 20-26 hour that circulates again, then forwards subsequent processing to;
(7) reel: during assembling, diaphragm clip is stacked between positive/negative plate, be wound on the pin with average tensile force, will roll up the core winding with adhesive tape after the winding and wrap;
(8) assembling: the volume core anode ear that will spool adopts supersonic welder to be welded on the plus plate current-collecting body aluminium strip; Negative pole lug welding is on negative current collector nickel strap or copper strips; Then pack into and roll up core supplementary module and the housing of packing into, adopt Laser Welding or supersonic welding to be connected with the anode collection post of cover plate the plus plate current-collecting body aluminium strip again, adopt Laser Welding or supersonic welding to be connected with the negative pole currect collecting post of cover plate negative current collector nickel strap or copper strips; At last with cover plate and housing seal welding;
(9) fluid injection: in the liquid injection hole of cover plate, carry out fluid injection.
11. the preparation method according to aforementioned LiMn2O4 aluminum hull rectangular cell claimed in claim 10 is characterized in that, and is further comprising the steps of after the fluid injection:
(10) change into: must change into by Over-The-Counter in 24 ~ 48 hours after the fluid injection, at first the electric current with 0.02C-0.05C is charged to voltage 3.4V in advance, and then the current charges with 0.2C transfers constant voltage charge to 4.2V, termination electric current 0.02C-0.05C; Be discharged to 3.0V with 0.2C again after being full of, the electric current with 0.5C discharges and recharges once again, with the discharge capacity of the 0.5C capacity that changes into as battery.
12. the preparation method according to aforementioned LiMn2O4 aluminum hull rectangular cell claimed in claim 10, it is characterized in that: in preparation cathode size process, when use comprises the binding agent of CMC, first CMC is added deionized water for stirring, adding conductive agent continues to stir again, then add native graphite and stir, add at last other binding agent and stir into slurry.
13. the preparation method according to aforementioned LiMn2O4 aluminum hull rectangular cell claimed in claim 10 is characterized in that: positive/negative plate is all taked Double-pole lug.
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| CN105591111A (en) * | 2015-12-16 | 2016-05-18 | 曙鹏科技（深圳）有限公司 | Battery slurry of lithium ion battery, preparation method thereof, electrode and battery |
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