CN102881947A - Lithium manganese oxide soft package battery and preparation method thereof - Google Patents
Lithium manganese oxide soft package battery and preparation method thereof Download PDFInfo
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- CN102881947A CN102881947A CN2012103827568A CN201210382756A CN102881947A CN 102881947 A CN102881947 A CN 102881947A CN 2012103827568 A CN2012103827568 A CN 2012103827568A CN 201210382756 A CN201210382756 A CN 201210382756A CN 102881947 A CN102881947 A CN 102881947A
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- volume core
- limn2o4
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- lug
- package battery
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title abstract 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
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- 238000012856 packing Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 230000004888 barrier function Effects 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 40
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 36
- -1 polypropylene Polymers 0.000 claims description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004743 Polypropylene Substances 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000000084 colloidal system Substances 0.000 claims description 22
- 229920001155 polypropylene Polymers 0.000 claims description 18
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 238000012710 chemistry, manufacturing and control Methods 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 238000004806 packaging method and process Methods 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 239000011230 binding agent 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
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004568 cement Substances 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000005096 rolling process Methods 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
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000004804 winding 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 4
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
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- 239000007767 bonding agent Substances 0.000 abstract 2
- 239000011888 foil Substances 0.000 abstract 1
- 238000001802 infusion Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
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- 238000005213 imbibition Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 238000004146 energy storage Methods 0.000 description 1
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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
Abstract
The invention relates to a lithium manganese oxide soft package battery and a preparation method thereof. A lithium manganese oxide material, a conducting agent, a bonding agent and the like are mixed to form positive slurry. Graphite, a conducting agent, a bonding agent and the like are mixed to form negative slurry. The positive slurry is coated on an aluminum foil to manufacture a positive plate, and the negative slurry is coated on a copper foil to manufacture a negative plate. Films are added into the positive plate and the negative plate to be rolled to form a cylindrical roll core, the roll core, a roll core auxiliary module, tab fixing pieces, outer tabs and an aluminum plastic film packing material are assembled, then infusion is performed, and finally sealing is performed. The preparation method maintains the characteristics including mature process and high efficiency of a cylindrical battery manufacture process and simultaneously has the advantages of being low in soft package battery cost and good in safety performance.
Description
Technical field
The invention belongs to the LiMn2O4 soft-package battery in lithium ion battery field, particularly Small And Medium Capacity and preparation method thereof.
Technical background
Lithium ion battery has been applied to the fields such as energy storage and power more and more with its high voltage, high-energy-density, the good advantages such as cycle performance.At present common lithium ion battery mainly contains case lithium ion battery outside metal shell lithium ion battery and the rigid plastics from the shell classification, and this class battery improper use easily produces blast, and cost is high; Classifying from battery core assembling mode mainly contains takeup type and stacked two classes, and takeup type battery core (being commonly referred to the volume core) and lamination type electric core are compared, and the takeup type technical maturity is stablized, and production cost is low, and production efficiency is high; And stacked technological process is complicated, and production efficiency is low.Takeup type technique also has its limitation in addition, can not do greatly such as capacity, and reason is that the coiling difficulty increases, rolls up degradation unfavorable factor appearance under the core degree of registration when pole piece is long.The takeup type cylindrical lithium ion battery of metal shell (take box hat 18650 cylindrical batteries as example) particularly, need to carry out a series of complicated technology flow processs such as negative lug and housing bottom welding, slot rolling, positive pole ear and block welding, sealing, increase production cost.
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
Purpose of the present invention is exactly the problem that exists for prior art, and the combination of a kind of employing takeup type volume core unit is provided, and the capacity adjusting range is large, process stabilizing, production cost are low, takes into account LiMn2O4 soft-package battery of explosion-resistance characteristic and preparation method thereof.
Technical scheme of the present invention comprises:
A kind of LiMn2O4 soft-package battery, comprise shell, outer lug, volume core and electrolyte, it is characterized in that: the volume core is to be connected to form by a plurality of volume core units, a plurality of volume core units are gripped therein by two volume core supplementary modules, shell adopts the aluminum plastic film soft packaging bag, two sealed sack places that are bonded in the aluminum plastic film soft packaging bag of outer lug, the lug of all volume core units is connected with outer lug by corresponding both positive and negative polarity collector; Described volume core unit is reeled by positive plate, barrier film and negative plate and is formed, and positive plate is the anode sizing agent take LiMn2O4 as main component to be coated on the aluminium foil make, and negative plate is cathode size to be coated on the Copper Foil make; Described plus plate current-collecting body is aluminium strip, and negative current collector is copper strips or nickel strap.
Described volume core supplementary module compound mode comprises: a kind of is that two volume core supplementary modules are along the axially rectangular structure to being combined into of volume core, its 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; Another kind is that two volume core supplementary modules are along the rectangular structure of neighboring to being combined into of volume core, its 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, volume core supplementary module is provided with inside and outside through hole or the groove that connects, and 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 volume core supplementary module is that the soft rubber material of PP material or electrolyte resistance corrosion is made; Described volume core supplementary module arranges slot at its blind end, and plus plate current-collecting body, negative current collector are pegged graft respectively and be fixed in end slot corresponding to volume core supplementary module.
Such scheme also comprises, is shaped with in advance the lug connecting plate on the sack encapsulating face of lug and aluminum plastic film outer packaging bag outside, and the lug connecting plate is to be made by the PP material.
Described anode sizing agent is to be the slurry that 5 ~ 7 parts binding agent, 87 ~ 91 parts LiMn2O4,2 ~ 3 parts conductive carbon black, 2 ~ 3 parts electrically conductive graphite and METHYLPYRROLIDONE reconcile into solid content 55 ~ 70% with weight portion; Described cathode size is to be the slurry that 89 ~ 93 parts graphite, 1 ~ 2 part conductive black, 1 ~ 2 part electrically conductive graphite, 5 ~ 7 parts binding agent and deionized water reconcile into solid content 30 ~ 50% with weight portion.
Described binding agent comprises: polyvinylidene fluoride or water-base cement, or the mixture of the butadiene-styrene rubber of the CMC of 1 ~ 2 part of weight portion and 4 ~ 5 parts, or CMC, 2 ~ 2.5 parts butadiene-styrene rubber and 2 ~ 2.5 parts the water-base cement mixture of 1 ~ 2 part of weight portion.
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.
Preparation method according to aforesaid LiMn2O4 soft-package battery may further comprise the steps:
(1) batching: the preparation of anode sizing agent is after LiMn2O4, conductive carbon black, electrically conductive graphite are all toasted, binding agent is added METHYLPYRROLIDONE to be stirred, add conductive black and electrically conductive graphite and continue to stir, add at last the slurry that LiMn2O4 stirs into thickness; The preparation of cathode size is described material stirring form slurry;
(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 is 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 and 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: stack successively in the middle of barrier film is placed 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 and is ultrasonically bonded on the plus plate current-collecting body aluminium strip; Negative electrode lug adopts and is ultrasonically bonded on negative current collector nickel strap or the copper strips, again plus plate current-collecting body, negative current collector are carried out ultrasonic bonding with outer lug respectively, the volume core is packed into and is rolled up the core supplementary module, plus plate current-collecting body, negative current collector are inserted respectively in draw-in groove corresponding to volume core supplementary module, in the aluminum plastic film packaging bag of packing at last;
(9) fluid injection, change into: be internalized 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 transfers constant voltage charge with the current charges of 0.2C to 4.2V, stops 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;
(10) gas in the battery is discharged after changing into, aluminum plastic film packing bag mouth and outer lug, outer lug stator are passed through the adhesive hot sealing.
The preparation method of aforesaid LiMn2O4 soft-package battery further comprises: in the anode sizing agent process for preparation of step (1), when selecting polyvinylidene fluoride as binding agent, first polyvinylidene fluoride being added METHYLPYRROLIDONE stirs, then add conductive black and electrically conductive graphite and continue to stir, add at last the slurry that LiMn2O4 stirs into thickness.In the cathode size process for preparation of step (1), when selecting CMC and butadiene-styrene rubber or CMC and butadiene-styrene rubber, water-base cement as binding agent, first CMC is added deionized water for stirring, adding conductive black and electrically conductive graphite continues to stir again, then add graphite and stir, add at last butadiene-styrene rubber or butadiene-styrene rubber and the water-base cement emulsion stirs into slurry.Positive/negative plate welding pure nickel material in the step (5) or the lug number of pure aluminum material are no less than two.
LiMn2O4 soft-package battery of the present invention, the mode that has at first adopted a plurality of volume cores to make up can be by the capacity of combination adjustment battery, the restriction that has solved single volume core capacity of lithium ion battery; The shell that next has adopted the aluminum plastic film flexible package has well solved the hidden peril of explosion that the hard shell battery exists, and security performance is better than the lithium ion battery of metal shell; Cost also is significantly less than the lithium ion battery of metal shell after its three raw material optimum organization.The preparation method that the present invention provides is that its production technology is relatively simple to further the optimizing of the characteristics of coiled battery technique, and production stability, fail safe and efficient all have greatly improved, and can satisfy multiple Small And Medium Capacity specification need of production.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 be a kind of LiMn2O4 soft-package battery partly cut open structural representation.
Fig. 2 is a kind of volume core supplementary module three-view diagram, and wherein Fig. 2 a is right view, and Fig. 2 b is front view, and Fig. 2 c is vertical view.
Fig. 3 is another kind of volume core supplementary module and volume core assembling schematic diagram.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention; technical scheme in the embodiment of the invention is clearly and completely described; 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.
Wherein, anode sizing agent is to be the slurry that 5 parts polyvinylidene fluoride, 90 parts LiMn2O4,2 parts conductive carbon black, 3 parts electrically conductive graphite and METHYLPYRROLIDONE reconcile into solid content 60% with weight portion; Described cathode size is to be 92 parts graphite, 1 part conductive black, 1.5 parts electrically conductive graphite, 1.5 CMCs, 2 parts butadiene-styrene rubber and 2 parts of water-base cements reconcile into solid content 40% with deionized water slurry with weight portion.
The preparation method of aforesaid LiMn2O4 soft-package battery may further comprise the steps:
(1) batching: the preparation of anode sizing agent is after LiMn2O4, conductive carbon black, electrically conductive graphite are all toasted, first polyvinylidene fluoride being added METHYLPYRROLIDONE stirs, then add conductive black and electrically conductive graphite and continue to stir, add at last the slurry that LiMn2O4 stirs into thickness.In the cathode size process for preparation, first CMC is added deionized water for stirring, add again conductive black and electrically conductive graphite and continue to stir, then add graphite and stir, add at last butadiene-styrene rubber and the water-base cement emulsion stirs into slurry.
(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 is as the lug district.
(3) baking: pole coating is complete to be toasted first afterwards, and the circulation baking forwarded subsequent processing to after 24 hours in vacuum oven.
(4) roll-in: positive and 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 the complete baking 24 hours that circulates again, then forwards subsequent processing to.
(7) reel: stack successively in the middle of barrier film is placed 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 and is ultrasonically bonded on the plus plate current-collecting body aluminium strip; Negative electrode lug adopts and is ultrasonically bonded on negative current collector nickel strap or the copper strips, again plus plate current-collecting body, negative current collector are carried out ultrasonic bonding with outer lug respectively, the volume core is packed into and is rolled up the core supplementary module, plus plate current-collecting body, negative current collector are inserted respectively in draw-in groove corresponding to volume core supplementary module, in the aluminum plastic film packaging bag of packing at last.
(9) fluid injection, change into: be internalized in 30 hours after the fluid injection, at first the electric current with 0.02C-0.05C is charged to voltage 3.4V in advance, then transfers constant voltage charge with the current charges of 0.2C to 4.2V, stops 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.
(10) gas in the battery is discharged after changing into, aluminum plastic film packing bag mouth and outer lug, outer lug stator are passed through the adhesive hot sealing.
Anode sizing agent is to be the butadiene-styrene rubber of 1.5 parts CMC and 4.5 parts, 88.5 parts LiMn2O4,3 parts conductive carbon black, 2.5 parts electrically conductive graphite reconcile into solid content 50% with deionized water slurry with weight portion; Cathode size is to be that to reconcile into solid content with METHYLPYRROLIDONE be 55% slurry for 89.5 parts graphite, 2 parts conductive black, 2 parts electrically conductive graphite, 6.5 parts polyvinylidene fluoride with weight portion.
The preparation method of the LiMn2O4 soft-package battery of the present embodiment and embodiment's 1 is basic identical, the one, distinguish to some extent in the batching link: the preparation of anode sizing agent is that LiMn2O4, conductive carbon black, electrically conductive graphite all do not need baking, CMC and butadiene-styrene rubber are added deionized water and stirring, add conductive black and electrically conductive graphite and continue to stir, add at last the slurry that LiMn2O4 stirs into thickness; The preparation of cathode size is described material stirring form slurry.The 2nd, suitably be adjusted into 25 hours at stoving time.The 3rd, the time that changes into after fluid injection can suitably be adjusted.
The scope that anode sizing agent and cathode size configuration and preparation method provide according to technical solution of the present invention is selected and is adjusted, and all can well realize purpose of the present invention, sets forth no longer one by one.
Again illustrate by above-described embodiment: employing be the combination of the coiled volume core unit of cylinder, volume core supplementary module is protected, and uses aluminum plastic film material outer package, has greatly improved fail safe and the economy of battery.
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.
Embodiment 6
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.
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.
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.
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.
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. LiMn2O4 soft-package battery, comprise shell, outer lug, volume core and electrolyte, it is characterized in that: the volume core is to be connected to form by a plurality of volume core units, a plurality of volume core units are gripped therein by two volume core supplementary modules, shell adopts the aluminum plastic film soft packaging bag, two sealed sack places that are bonded in the aluminum plastic film soft packaging bag of outer lug, the lug of all volume core units is connected with outer lug by corresponding both positive and negative polarity collector; Described volume core unit is the cylindrical roll core of being reeled and being formed by positive plate, barrier film and negative plate, and positive plate is to be that the anode sizing agent of main component is coated on the aluminium foil and makes with LiMn2O4, and negative plate is cathode size to be coated on the Copper Foil make; Described plus plate current-collecting body is aluminium strip, and negative current collector is copper strips or nickel strap.
2. LiMn2O4 soft-package battery according to claim 1, it is characterized in that: described volume core supplementary module compound mode comprises: a kind of is that two volume core supplementary modules are along the axially rectangular structure to being combined into of volume core, its 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; Another kind is that two volume core supplementary modules are along the rectangular structure of neighboring to being combined into of volume core, its 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, volume core supplementary module is provided with inside and outside through hole or the groove that connects, and 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 volume core supplementary module is that the soft rubber material of PP material or electrolyte resistance corrosion is made; Described volume core supplementary module arranges slot at its blind end, and plus plate current-collecting body, negative current collector are pegged graft respectively and be fixed in end slot corresponding to volume core supplementary module.
3. LiMn2O4 soft-package battery according to claim 1 and 2, it is characterized in that: be shaped with in advance the lug connecting plate on the sack encapsulating face of lug and aluminum plastic film outer packaging bag outside, the lug connecting plate is to be made by the PP material.
4. LiMn2O4 soft-package battery according to claim 1 and 2 is characterized in that: described anode sizing agent is to be that to reconcile into solid content be 55 ~ 70% slurry for 5 ~ 7 parts binding agent, 87 ~ 91 parts LiMn2O4,2 ~ 3 parts conductive carbon black, 2 ~ 3 parts electrically conductive graphite and METHYLPYRROLIDONE with weight portion; Described cathode size is to be the slurry that 89 ~ 93 parts graphite, 1 ~ 2 part conductive black, 1 ~ 2 part electrically conductive graphite, 5 ~ 7 parts binding agent and deionized water reconcile into solid content 30 ~ 50% with weight portion.
5. LiMn2O4 soft-package battery according to claim 4, it is characterized in that: described binding agent comprises: polyvinylidene fluoride or water-base cement, or the mixture of the butadiene-styrene rubber of the CMC of 1 ~ 2 part of weight portion and 4 ~ 5 parts, or CMC, 2 ~ 2.5 parts butadiene-styrene rubber and 2 ~ 2.5 parts the water-base cement mixture of 1 ~ 2 part of weight portion.
6. LiMn2O4 soft-package battery 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.
7. LiMn2O4 soft-package battery according to claim 6, it is characterized in that: 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%; The weight of described inorganic filler accounts for the 30%-100% of coated polymeric colloidal materials weight.
8. LiMn2O4 soft-package battery 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 soft-package battery 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 soft-package battery of the arbitrary claim of 4-9, it is characterized in that: may further comprise the steps:
(1) batching: the preparation of anode sizing agent is after LiMn2O4, conductive carbon black, electrically conductive graphite are all toasted, binding agent is added METHYLPYRROLIDONE to be stirred, add conductive black and electrically conductive graphite and continue to stir, add at last the slurry that LiMn2O4 stirs into thickness; The preparation of cathode size is described material stirring form slurry;
(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 is 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 and 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: stack successively in the middle of barrier film is placed 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 and is ultrasonically bonded on the plus plate current-collecting body aluminium strip; Negative electrode lug adopts and is ultrasonically bonded on negative current collector nickel strap or the copper strips, again plus plate current-collecting body, negative current collector are carried out ultrasonic bonding with outer lug respectively, the volume core is packed into and is rolled up the core supplementary module, plus plate current-collecting body, negative current collector are inserted respectively in draw-in groove corresponding to volume core supplementary module, in the aluminum plastic film packaging bag of packing at last;
(9) fluid injection, change into: be internalized 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 transfers constant voltage charge with the current charges of 0.2C to 4.2V, stops 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;
(10) gas in the battery is discharged after changing into, aluminum plastic film packing bag mouth and outer lug, outer lug stator are passed through the adhesive hot sealing.
11. the preparation method of LiMn2O4 soft-package battery according to claim 10, it is characterized in that: in the anode sizing agent process for preparation of step (1), when selecting polyvinylidene fluoride as binding agent, first polyvinylidene fluoride being added METHYLPYRROLIDONE stirs, then add conductive black and electrically conductive graphite and continue to stir, add at last the slurry that LiMn2O4 stirs into thickness.
12. the preparation method of LiMn2O4 soft-package battery according to claim 10, it is characterized in that: in the cathode size process for preparation of step (1), when selecting CMC and butadiene-styrene rubber or CMC and butadiene-styrene rubber, water-base cement as binding agent, first CMC is added deionized water for stirring, adding conductive black and electrically conductive graphite continues to stir again, then add graphite and stir, add at last butadiene-styrene rubber or butadiene-styrene rubber and the water-base cement emulsion stirs into slurry.
13. according to claim 10, the preparation method of 11 or 12 described LiMn2O4 soft-package batteries, it is characterized in that: the positive/negative plate welding pure nickel material in the step (5) or the lug number of pure aluminum material are no less than two.
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