CN102420312A - High-voltage lithium ion battery, composite electrode couple and preparation methods of high-voltage lithium ion battery and composite electrode couple - Google Patents
High-voltage lithium ion battery, composite electrode couple and preparation methods of high-voltage lithium ion battery and composite electrode couple Download PDFInfo
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- CN102420312A CN102420312A CN201110344610XA CN201110344610A CN102420312A CN 102420312 A CN102420312 A CN 102420312A CN 201110344610X A CN201110344610X A CN 201110344610XA CN 201110344610 A CN201110344610 A CN 201110344610A CN 102420312 A CN102420312 A CN 102420312A
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- lithium ion
- combination electrode
- current collector
- adhesive
- composite current
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
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- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
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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
Abstract
The invention discloses a high-voltage lithium ion battery, a composite electrode couple and preparation methods of the high-voltage lithium ion battery and the composite electrode couple, which belong to the technical field of lithium ion batteries. The composite electrode couple provided by the invention comprises a porous diaphragm, an anode mixture and a cathode mixture; one surface of the porous diaphragm is coated with the anode mixture which comprises an anode active material, a conductive agent and an adhesive; and the other surface of the porous diaphragm is coated with the cathode mixture which comprises a cathode active material, the conductive agent and the adhesive. The high-voltage lithium ion battery provided by the invention comprises the composite electrode couple, a composite current collector and an electrolyte, wherein a block body is formed by alternately superposing a plurality of composite electrode couples and composite current collectors; the composite electrode couples in the block body are soaked in the electrolyte; an electronic conductive adhesive layer with the thickness being less than 10 microns is arranged between each composite electrode couple and each composite current collector; and the composite current electrodes are arranged on the upper surface and the lower surface of the block body. The high-voltage lithium ion battery provided by the invention has the advantages of high voltage, good safety, good consistency and the like.
Description
Technical field
The invention belongs to technical field of lithium ion, the high-voltage lithium ion batteries, combination electrode that relates in particular to a kind of electric vehicle to and preparation method thereof.
Background technology
As an importance of Future New Energy Source development, the extensive development of electric automobile is an inexorable trend.Lithium ion battery receives much concern as the used for electric vehicle electrokinetic cell because lithium ion battery have high-energy-density, operating voltage high, have extended cycle life, advantages such as self discharge is low, memory-less effect.Yet, the fail safe of present used for electric vehicle electrokinetic cell and the technical bottleneck that consistency problem has become the ev industry scale development.
Inner stack series connection electrode preparation high-voltage lithium ion batteries is that of the problems referred to above solves thinking preferably.But in the existing lithium ion battery manufacturing process, electrode active material is coated on the collector, carries out dry compressing tablet then, and compressing tablet pressure is generally at 6～20MPa.What the collector of internal series-connection high-voltage lithium ion batteries generally adopted is copper aluminum composite foil film; The paper tinsel film thickness is less than 100 microns; If adopt traditional electrode coating and compressing tablet mode to be difficult to avoid composite current collector is crushed; And composite current collector will be short-circuited between the adjacent cell of high-voltage lithium ion batteries inside in case quilt crushes and crackle occurs.Therefore be necessary to seek a kind of new high-voltage lithium ion batteries structure and the new production method of avoiding composite current collector is carried out direct tablet compressing.
Summary of the invention
Be to solve the problems referred to above that high-voltage lithium ion batteries exists, the present invention provides a kind of and electrode active material directly is coated on porous septum is prepared into the right technology of combination electrode, and is applied to the making of novel high-voltage lithium ion batteries.
The present invention adopts following technical scheme:
High-voltage lithium ion batteries of the present invention by combination electrode to 4, electron conduction adhesive layer 6, composite current collector 5, lug, electrolyte, shell constitute.Described combination electrode comprises porous septum 1, cathode mix 2 and negative pole mixture 3 to 4; The one side of this porous septum 1 is coated with the cathode mix 2 that comprises positive electrode active materials, conductive agent and adhesive; Another side is coated with the negative pole mixture 3 that comprises negative active core-shell material, conductive agent and adhesive, has constituted described combination electrode together to 4.Said combination electrode all has the white space of a width greater than the uncoated active material of 5mm to 4 edges.Said combination electrode to 4 and composite current collector 5 between an electron conduction adhesive layer 6 is arranged, make a plurality of combination electrodes to 4 with composite current collector 5 replace the bonding block that becomes.Composite current collector 5 is a slice composite metallic material film, and the composite metallic material film is made up of less than 50 microns Copper Foil is compound the aluminium foil and the thickness of thickness less than 50 microns, and compound mode includes but not limited to plating, electrochemistry plating, vapor deposition, gluing and pressurize rolling.
Said porous septum 1 material is polyethylene, polypropylene, Kynoar or the nonconducting porous polymer material of other electronics; Perhaps, described porous septum 1 material is the composite porous material of glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or nonconducting Inorganic Non-metallic Materials of other electronics and organic polymer.
Described positive electrode active materials is the LiFePO 4 (LiFePO that contains lithium
4), doped lithium manganese oxide (Li
0.9～1.2M
0～0.2Mn
2O
4, M is one or more elements among Na, Mg, Ca, Ni, the Co), lithium and cobalt oxides (LiCoO
2), lithium-nickel-cobalt-oxygen thing (LiNi
0.8Co
0.2O
2), lithium-nickel-manganese-cobalt oxidation thing (LiNi
1/3Mn
1/3Co
1/3O
2Or LiNi
2/5Mn
2/5Co
1/5O
2) and other contain one or more mixtures of lithium metal oxide; Described negative active core-shell material be can reversible embedding lithium acieral, silicon-base alloy, kamash alloy, Li-Ti oxide (Li
4Ti
5O
12), one or more mixtures of material with carbon element; Described conductive agent is one or more mixtures in carbon black, carbon fiber, the metallic particles.Described adhesive is one or more mixtures of Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, starch, CMC, regenerated cellulose, polyethylene glycol oxide, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene ethylene propylene diene rubber, butadiene-styrene rubber, fluorubber, epoxy resin, phenolic resins and all kinds of synthetic adhesive materials.
Said combination electrode is characterized in that 4 preparation method: positive electrode active materials, conductive agent, adhesive being mixed in obtaining anode sizing agent in the solvent earlier, coat the one side of said porous septum 1, is 60～110 ℃ of scope inner dryings in temperature; Again negative active core-shell material, conductive agent, adhesive are mixed in and obtain cathode size in the solvent; Coat the another side of porous septum 1; In temperature is 60～110 ℃ of scope inner dryings, and compressing tablet in pressure is 6～20MPa scope makes combination electrode to 4 after the cutting then; Perhaps, negative active core-shell material, conductive agent, adhesive being mixed in obtaining cathode size in the solvent earlier, coat the one side of said porous septum 1, is 60～110 ℃ of scope inner dryings in temperature; Again positive electrode active materials, conductive agent, adhesive are mixed in and obtain anode sizing agent in the solvent; Coat the another side of porous septum 1; In temperature is 60～110 ℃ of scope inner dryings, and compressing tablet in pressure is 6～20MPa scope makes combination electrode to 4 after the cutting then.
The preparation method of said high-voltage lithium ion batteries comprises following steps: a, preparation combination electrode are to 4; B, conductive agent and adhesive are mixed in the solvent, process slurry, be coated in combination electrode 4 two sides is formed thickness less than 10 microns electron conduction adhesive layer 6; C, a plurality of two sided coatings are had an electron conduction adhesive layer 6 combination electrode to 4 and alternately stack of composite current collector 5; And respectively combination electrode is coated with the surface of positive electrode active materials 2 and the bonding foil of composite current collector 5 to 4; It is bonding that combination electrode is coated with the Copper Foil of surface and composite current collector 5 of negative active core-shell material 3 to 4; Process a block, the upper and lower surfaces of block is a composite current collector 5; After d, above-mentioned block vacuumize drying; Exert pressure less than the pressure of 6MPa and inject electrolyte at the upper and lower surfaces of block; Adopt dielectric adhesive 7 with bonding sealing in the edge of composite current collector 5 and mutually insulated then; And anodal 8 (the aluminium foil one sides of surface recombination collector) in the surface of block are connected with positive pole ear 9, the surperficial negative pole 10 of block (the Copper Foil one side of surface recombination collector) is connected with negative lug 11, cleans and wraps up shell formation high-voltage lithium ion batteries after encapsulating.
Dielectric adhesive in the said steps d is: one or more in epoxy acrylate, polyurethane acrylic resin, polyester acrylic resin, aminoacrylic acid resin, epoxy resin, phenolic resins, furane resins, polybutadiene, organic siliconresin or the rubber-based resin.Described solvent is: one or more in the derivative of deionized water, isopropyl alcohol, N-methyl pyrrolidone, dimethylformamide and dimethylacetylamide or above-mentioned material.
Technical advantage of the present invention is embodied in:
1, electrode active material directly is coated on porous septum after dry, that compressing tablet directly is prepared into combination electrode is right; Compressing tablet causes the local damage of collector and the problem of asymmetric bending after can avoiding electrode active material is coated on composite current collector, thereby has avoided causing because of the collector breakage potential safety hazard of high-voltage lithium ion batteries internal short-circuit;
2, adopt the electron conduction adhesive layer that combination electrode pair is bonded as one with composite current collector, improved the dynamic conformance and the fail safe of electrokinetic cell use.
Description of drawings
Fig. 1 is the right structural representation of combination electrode, among the figure: the 1--porous septum; The 2--cathode mix; 3--negative pole mixture.
Fig. 2 is the high-voltage lithium ion batteries structural representation, and wherein Fig. 2 a is a cut-away view, and Fig. 2 b is the external structure end view; Among the figure: the 4--combination electrode is right, 5--composite current collector, 6--electron conduction adhesive layer; The 7--dielectric adhesive, the 8--surface is anodal, the 9--positive pole ear; 10--surface negative pole, the 11--negative lug.
Embodiment
Embodiment one:
The preparation that combination electrode is right: with polyethylene glycol oxide, LiFePO
4/ C and carbon black consist of adhesive by weight percentage: carbon black: LiFePO
4/ C=8: be mixed at 7: 85 and obtain anode sizing agent in the deionized water, this slurry is evenly coated surfaces coated be covered with one deck inorganic nano-particle (thickness is less than 5 microns, and inorganic nano-particle is SiO
2, Al
2O
3, TiO
2Deng) the one side of nonwoven fabrics porous septum, 80 ℃ of oven dry down; Again with sodium carboxymethylcellulose, carbon black, Li
4Ti
5O
12(lithium titanate) consists of Li by weight percentage
4Ti
5O
12: carbon black: adhesive=90: 3: 7 is mixed in and obtains cathode size in the deionized water, this slurry is evenly coated surfaces coated be covered with one deck inorganic nano-particle (thickness is less than 5 microns, and inorganic nano-particle is SiO
2, Al
2O
3, TiO
2Deng) the another side of nonwoven fabrics porous septum, 80 ℃ of oven dry down, compressing tablet in pressure is 6～20MPa scope then, it is right to make combination electrode after the cutting.
The preparation of electron conduction adhesive layer: carbon black and polyethylene glycol oxide are carbon black by weight percentage: polyethylene glycol oxide=be mixed in deionized water at 7: 3; Process slurry, be coated in the right two sides of combination electrode and form thickness less than 10 microns electron conduction adhesive layer.
The combination electrode that 10 two sided coatings is had the electron conduction adhesive layer is to alternately superposeing with 11 composite current collectors; And respectively with combination electrode to the surface that is coated with positive electrode active materials and the bonding foil of composite current collector; Combination electrode is bonding to the Copper Foil of the surface that is coated with negative active core-shell material and composite current collector; Process a block, the upper and lower surfaces of block is a composite current collector, vacuumize drying after; Exert pressure less than the pressure of 6MPa and inject electrolyte at the upper and lower surfaces of block; Adopt dielectric adhesive with bonding sealing in the edge of composite current collector and mutually insulated then, and the surface of block anodal (the aluminium foil one side of composite current collector) is connected with positive pole ear, the surperficial negative pole of block (the Copper Foil one side of composite current collector) is connected with negative lug; Clean encapsulation back parcel shell, obtain the high-voltage lithium ion batteries that operating voltage is about 20V.
Embodiment two:
The preparation that combination electrode is right: PVDF (Kynoar), modification LiMn2O4 and carbon black are consisted of adhesive by weight percentage: carbon black: LiMn2O4=be mixed in NMP (N-methyl pyrrolidone) at 8: 7: 85 fully is mixed and made into anode sizing agent.This slurry is evenly coated the one side of polyolefin porous barrier film ,-60～110 ℃ of oven dry; PVDF, lithium titanate and carbon black are consisted of lithium titanate by weight percentage: carbon black: adhesive=be mixed in NMP at 90: 3: 7; Fully be mixed and made into cathode size; Again this slurry is uniformly coated on the another side of polyolefin porous barrier film; 60～110 ℃ of oven dry, compressing tablet in pressure is 6～20MPa scope then, it is right to make combination electrode after the cutting.
The preparation of electron conduction adhesive layer: PVDF and carbon black percentage by weight are consisted of carbon black: PVDF=7: 3 are dissolved among the NMP, process slurry, are coated in the right two sides of combination electrode and form thickness less than 10 microns electron conduction adhesive layer.
The combination electrode that 50 two sided coatings is had the electron conduction adhesive layer is to alternately superposeing with 51 composite current collectors; And respectively with combination electrode to the surface that is coated with positive electrode active materials and the bonding foil of composite current collector; Combination electrode is bonding to the Copper Foil of the surface that is coated with negative active core-shell material and composite current collector; Process a block, the upper and lower surfaces of block is a composite current collector, vacuumize drying after; Exert pressure less than the pressure of 6MPa and inject electrolyte at the upper and lower surfaces of block; Adopt dielectric adhesive with bonding sealing in the edge of composite current collector and mutually insulated then, and the surface of block anodal (the aluminium foil one side of composite current collector) is connected with positive pole ear, the surperficial negative pole of block (the Copper Foil one side of composite current collector) is connected with negative lug; Clean encapsulation back parcel shell, obtain the high-voltage lithium ion batteries that working voltage platform is approximately 125V.
The specific embodiment of the invention is not in order to limit the present invention.Any those of ordinary skill in the art; Do not breaking away under the technical scheme scope situation of the present invention; All the method for above-mentioned announcement capable of using and technology contents are made many possible changes and modification to technical scheme of the present invention, or are revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical scheme of the present invention, all still belongs in the scope of technical scheme protection of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (10)
1. the combination electrode of a high-voltage lithium ion batteries is right; It is characterized in that: comprise porous septum, cathode mix and negative pole mixture; The one side of said porous septum is coated with the cathode mix that comprises positive electrode active materials, conductive agent and adhesive; Another side is coated with the negative pole mixture that comprises negative active core-shell material, conductive agent and adhesive, and the uncoated white space of width greater than 5mm left in the edge of said porous septum.
2. combination electrode as claimed in claim 1 is right; It is characterized in that: said porous septum material is polyethylene, polypropylene, Kynoar or the nonconducting porous polymer material of other electronics; Perhaps, said porous septum material is the composite porous material of glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or nonconducting Inorganic Non-metallic Materials of other electronics and organic polymer.
3. combination electrode as claimed in claim 1 is right, it is characterized in that: said positive electrode active materials is that the LiFePO 4 that contains lithium, doped lithium manganese oxide, lithium and cobalt oxides, lithium-nickel-cobalt-oxygen thing, lithium-nickel-manganese-cobalt oxidation thing and other contain one or more mixtures of lithium metal oxide; Said negative active core-shell material is acieral, silicon-base alloy, kamash alloy, Li-Ti oxide that can reversible embedding lithium, one or more mixtures of material with carbon element; Said conductive agent is one or more mixtures in carbon black, carbon fiber, the metallic particles.
4. high-voltage lithium ion batteries; It is characterized in that; Comprise that combination electrode as claimed in claim 1 is to, composite current collector and electrolyte; Said composite current collector is a slice by thickness less than 50 microns aluminium foil and thickness less than the compound composite metallic material film that constitutes of 50 microns Copper Foil, a plurality of combination electrodes to composite current collector alternately stack constitute a block, a layer thickness is arranged less than 10 microns electron conduction adhesive layer between said combination electrode pair and the composite current collector; The upper and lower surface of above-mentioned block is a composite current collector, and the combination electrode of this block inside is to being immersed in the electrolyte.
5. high-voltage lithium ion batteries as claimed in claim 4; It is characterized in that: said electron conduction adhesive layer is the mixture of adhesive and metal or material with carbon element conductive agent; The mass percent of said conductive agent is greater than 60%, and said electron conduction adhesive layer thickness is less than 10 microns.
6. like the said high-voltage lithium ion batteries of claim 4, it is characterized in that: said adhesive is one or more mixtures of Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, starch, CMC, regenerated cellulose, polyethylene glycol oxide, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene ethylene propylene diene rubber, butadiene-styrene rubber, fluorubber, epoxy resin, phenolic resins and all kinds of composite insulation adhesive materials.
7. preparation method that combination electrode is right is characterized in that:
A, positive electrode active materials, conductive agent, adhesive be mixed in obtain anode sizing agent in the solvent, coat the one side of said porous septum, is 60～110 ℃ of scope inner dryings in temperature; Simultaneously, negative active core-shell material, conductive agent, adhesive being mixed in obtaining cathode size in the solvent, coat the another side of porous septum, is 60～110 ℃ of scope inner dryings in temperature;
B, in pressure is 6～20MPa scope compressing tablet, it is right to make combination electrode after the cutting.
8. the preparation method of a high-voltage lithium ion batteries, it is characterized in that: the method includes the steps of:
A, described in claim 7 method to prepare combination electrode right;
B, conductive agent and adhesive are mixed in the solvent, process slurry, be coated in the right two sides of combination electrode and form thickness less than 10 microns electron conduction adhesive layer;
C, a plurality of two sided coatings are had an electron conduction adhesive layer combination electrode to the alternately stack of a plurality of composite current collectors; And respectively with combination electrode to the surface that is coated with positive electrode active materials and the bonding foil of composite current collector; Combination electrode is bonding to the Copper Foil of the surface that is coated with negative active core-shell material and composite current collector; Process a block, the upper and lower surfaces of block is a composite current collector;
After d, above-mentioned block vacuumize drying; Apply less than the pressure of 6MPa and inject electrolyte at the upper and lower surfaces of block; Adopt dielectric adhesive with bonding sealing in the edge of composite current collector and mutually insulated then; And is connected with positive pole ear block surface is anodal, the block surface negative pole is connected with negative lug, cleans and wraps up shell formation high-voltage lithium ion batteries after encapsulating.
9. the preparation method described in claim 8, it is characterized in that: the dielectric adhesive in the said steps d is: one or more in epoxy acrylate, polyurethane acrylic resin, polyester acrylic resin, aminoacrylic acid resin, epoxy resin, phenolic resins, furane resins, polybutadiene, organic siliconresin or the rubber-based resin.
10. the preparation method described in claim 7 and claim 8, it is characterized in that: described solvent is: one or more in the derivative of deionized water, isopropyl alcohol, N-methyl pyrrolidone, dimethylformamide and dimethylacetylamide or above-mentioned material.
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