CN106025345B - A kind of lithium ion battery - Google Patents
A kind of lithium ion battery Download PDFInfo
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- CN106025345B CN106025345B CN201610524884.XA CN201610524884A CN106025345B CN 106025345 B CN106025345 B CN 106025345B CN 201610524884 A CN201610524884 A CN 201610524884A CN 106025345 B CN106025345 B CN 106025345B
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- arc oxidation
- lithium ion
- ion battery
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 61
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000010935 stainless steel Substances 0.000 claims abstract description 21
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 24
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011698 potassium fluoride Substances 0.000 claims description 10
- 235000003270 potassium fluoride Nutrition 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 230000002457 bidirectional effect Effects 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 39
- 229910052744 lithium Inorganic materials 0.000 abstract description 39
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 abstract description 5
- 230000002269 spontaneous effect Effects 0.000 abstract description 5
- 230000005611 electricity Effects 0.000 abstract description 4
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 41
- 239000010410 layer Substances 0.000 description 24
- 238000005524 ceramic coating Methods 0.000 description 14
- 239000011224 oxide ceramic Substances 0.000 description 12
- 229910052574 oxide ceramic Inorganic materials 0.000 description 12
- 238000007789 sealing Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 241000357293 Leptobrama muelleri Species 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000001192 hot extrusion Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910001234 light alloy Inorganic materials 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical group [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 2
- 239000001472 potassium tartrate Substances 0.000 description 2
- 229940111695 potassium tartrate Drugs 0.000 description 2
- 235000011005 potassium tartrates Nutrition 0.000 description 2
- ASHGTUMKRVIOLH-UHFFFAOYSA-L potassium;sodium;hydrogen phosphate Chemical compound [Na+].[K+].OP([O-])([O-])=O ASHGTUMKRVIOLH-UHFFFAOYSA-L 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium ion batteries, belong to field of material preparation.The lithium ion battery includes shell, and the basis material of the shell is magnesium alloy, and surface of shell has micro-arc oxidation ceramic layer.The micro-arc oxidation ceramic layer with a thickness of 5-40 μm, phase composition mainly includes magnesium fluoride and trifluoro magnesium potassium, PBR > 1 and a small amount of magnesia.The invention also discloses the preparation methods of battery case.Surface there is the magnesium alloy of micro-arc oxidation ceramic layer to be applied in lithium dynamical battery shell by the present invention, and battery case quality obtained reduces about 60% relative to stainless steel steel shell；The not spontaneous combustion within calcination 5 minutes at 1000 DEG C；It is tested through cycle charge-discharge 1000, Mg/Li electricity occurs to without obviously slotting lithium phenomenon.
Description
Technical field
The present invention relates to field of material preparation, and in particular to a kind of lithium ion battery.
Background technique
Lithium dynamical battery has operating voltage height, has extended cycle life, and the high feature of specific energy obtains in new-energy automobile field
To extensive use.Although lithium dynamical battery energy density has been greatly improved, still it is difficult to meet consumer couple
Power vehicle course continuation mileage demand.Current battery technological design relative maturity is anode, carbon with LiFePO4 and ternary material
Material is that the lithium-ion-power cell of cathode is difficult the breakthrough for having big in energy density, therefore, it is dynamic to find new way promotion lithium
The energy density of power battery is imperative.
Lithium dynamical battery generally uses stainless steel material to make battery case, and Stainless Steel Shell will account for battery core total weight
1/4~1/3 or so, stainless steel is substituted to mitigate the weight of battery case using light alloy material, is to improve power battery energy
One effective means of density.Aluminium alloy is more common light alloy material, there is data to suggest that with the aluminium of model power battery
Shell material weight compared with stainless steel case material will it is light more than half further, since aluminum hull material hardness is smaller work as cell internal pressure
When larger, it is easy to be released by aluminium shell, aluminum hull reacts more sharp for inner pressure of battery, and steel shell closes in contrast
Golden internally pressure is slow in reacting, therefore, the safety of power battery can be increased substantially using aluminium shell material.But aluminium
Shell easily corrodes, once shell corrosion will performance to battery and safety bring a negative impact, and aluminium alloy is normal at present
With process for treating surface (nickel plating, differential arc oxidation etc.), no matter it is not possible to reach from technical maturity or scale cost control
The needs of industrialized production.
Magnesium is most light one of metal, and relative density only has 1.74g/cm3, about the 2/3 of aluminium, the 1/4 of iron, have good
Good damping property, heat conductivity, electromagnetic wave shielding, machining property and reprocessing recycling characteristic.Therefore, it is replaced using magnesium alloy
For lithium dynamical battery stainless steel casing, and then battery specific energy is promoted, extends the course continuation mileage of power car.If directlying adopt magnesium
Alloy does lithium dynamical battery shell, and after cathode connection, magnesium sheath voltage is 0.3V (vs.Li+/ Li) nearby when, exist obvious
Slotting lithium behavior, charge efficiency can not only reduced and battery electrochemical capacity loss, while can also corrode magnesium alloy case；Separately
Outside, magnesium alloy belongs to combustible metal, and flame resistance experiment shows that thickness is less than 0.5mm magnesium alloy plate and can be ignited in 6s,
It burns when destroying, squeeze, puncturing if lithium battery is met with, easily causes the spontaneous combustion of magnesium alloy shell, and then aggravate lithium electricity
Combustion explosion, bring great hidden danger to the safety of power battery.
It can be seen that must first have to solve magnesium alloy and the slotting lithium of electrolyte generation as lithium dynamical battery using magnesium alloy
Electrochemistry capacitance problem is lost in behavior, prevents lithium battery and destroys the security risk that burning causes magnesium alloy spontaneous combustion.It not yet sends out at present
It now can satisfy the solution of requirements above.
Summary of the invention
The present invention provides a kind of lithium ion batteries, by carrying out super fine and close micro-arc oxidation treatment to magnesium alloy shell,
Mg alloy surface forms one layer of even compact oxidation ceramic layer, and magnesium alloy is overcome to be directly used as inserting existing for lithium dynamical battery shell
Lithium problem, while meeting the needs of lithium battery loss of weight, safety.
A kind of lithium ion battery, including shell, the basis material of the shell are magnesium alloy, and surface of shell has differential of the arc oxygen
Change ceramic layer.
The micro-arc oxidation ceramic layer with a thickness of 5-40 μm, phase composition mainly includes magnesium fluoride and trifluoro magnesium potassium, PBR
> 1 and a small amount of magnesia.
The present invention is by adjusting Microarc oxidation electrolyte formula, so that the main phase composition of micro-arc oxidation ceramic layer is fluorination
Object, instead of traditional magnesia ceramics coating.The main component magnesium fluoride of film layer not only PBR > 1, so that ceramic membrane compactness
The defects of height, hole and crackle, is few, has completely cut off the diffusive migration of electrolyte, and the crystal structure of ceramic membrane makes lithium ion can not
Insertion, to effectively inhibit the generation of slotting lithium behavior.In addition, film layer chemical stability with higher, even if lithium electricity matter is sent out
Raw a small amount of water suction is decomposed, and will not cause to ensure the inhibiting effect under actual environment to slotting lithium behavior to film layer corrosion failure.
Burn test results show that the magnesium alloy with micro-arc oxidation ceramic layer of the invention has (1000 DEG C of anti-flammability
Lower heating 5min is reactionless).Therefore, for the material as battery case, will not occur to go to pot because of battery causes transient temperature liter
Height leads to the case where shell spontaneous combustion, meets the requirement of lithium dynamical battery safety.
In addition, battery case of the invention is because the coating is uniform and compact, flat and smooth for arc differential oxide ceramic, with basal body binding force
Well, wearability with higher solves electrolyte in charge and discharge process and inhibits slotting lithium existing the etching problem of magnesium alloy
As.Charge-discharge test the result shows that, battery case of the invention is after undergoing 1000 cycle charge-discharges without obviously slotting lithium phenomenon
Occur.
The preparation method of the shell, comprising:
(1) magnesium alloy is processed into the casing of lithium ion battery base of cast；
(2) it by after the pretreatment of casing of lithium ion battery base, is placed in electrolyte and carries out micro-arc oxidation treatment, obtain surface tool
There is the casing of lithium ion battery of micro-arc oxidation ceramic layer；
(3) stainless steel substrates back cover is used, lithium-ion battery shell is made.
In battery case preparation of the present invention, magnesium alloy shell processing and forming is carried out first, then carries out mechanical grinding, chemistry throwing
Then the pretreatment such as light forms differential arc oxidation compactness ceramic coating on magnesium alloy shell surface using micro-arc oxidation treatment, most
Stainless steel back cover is carried out afterwards.
The magnesium alloy is AZ31B, AZ91B, WE43 or WE94, and raw material magnesium alloy is squeezed through multi-pass or punching press, preparation
Magnesium alloy thin-wall pipe out, tube wall thickness 0.4-5mm, outer diameter 10-100mm, then as needed by tubular object extruding at phase
Answer the battery case base of size.
The component of the electrolyte are as follows: potassium fluoride 10-40g/L, sodium metasilicate 10-50g/L, phosphate or sodium carbonate 5-20g/
L, sodium citrate, Boratex or tartrate 2-10g/L, remaining is water, pH value 3.5-9.0.
Potassium fluoride provides the fluorine ion in electrolyte, and concentration determines the content of magnesium fluoride in ceramic coating formed by micro-arc oxidation, adjusts
Whole concentration changes from 10g/L to 40g/L, reaches maximum value when concentration reaches 30g/L, further increases with concentration, film layer fluorination
The content of magnesium is held essentially constant.
The phosphate is potassium orthophosphate, potassium orthophosphate sodium, potassium phosphate,monobasic, disodium-hydrogen, potassium dihydrogen phosphate, phosphoric acid
One or more mixture in sodium dihydrogen, potassium tripolyphosphate or sodium tripolyphosphate；Carbonate is sodium carbonate or sodium bicarbonate；Wine
Stone hydrochlorate is potassium tartrate or sodium potassium tartrate tetrahydrate.The above-mentioned additive for electrolyte, influences the oxidation process of differential arc oxidation, to oxygen
The compactness for changing film has decisive action, adjusts the concentration of additive, the compactness of film layer can be improved.
Preferably, the component of the electrolyte are as follows: potassium fluoride 30g/L, sodium metasilicate 20g/L, phosphoric acid 5ml/L, di(2-ethylhexyl)phosphate
Hydrogen potassium 10g/L, Boratex 10g/L, remaining is water, pH=3.8-4.0.
The micro-arc oxidation treatment uses high frequency bidirectional pulse mode, frequency 100-1000Hz, current density 2-5A/
dm2, positive end voltage is 300-800V, and negative sense end voltage is 30-80V, and positive duty ratio is 10%-50%, negative sense duty ratio
For 10%-50%.Used high-frequency impulse has densification, and the micro-arc oxidation films by adjusting electrical parameter preparation are equal
It is even, consistency is high.
Preferably, frequency is 1000Hz, positive end voltage is 800V, and negative sense end voltage is 35V, current density 2A/
dm2, positive and negative pulsewidth is respectively 0.5ms and 0.4ms.
The condition of the micro-arc oxidation treatment: 15-50 DEG C of electrolyte temperature, oxidization time 20-45min.
Current density is adjusted from 2A/dm2To 5A/dm2, the growth rate of film layer can be improved, current density is bigger, film layer
It grows faster.Oxidization time is 20-45min, and with the extension of oxidization time, thicknesses of layers increases, by adjusting oxidization time,
It can get ceramic membrane of the thicknesses of layers range at 5-40 μm.Preferably, 25 DEG C of electrolyte temperature, oxidation processes 20min.
It is final to obtain super fine and close ceramic film by the adjustment of above-mentioned electrolyte and electrical parameter, make magnesium alloy power electric
Pond shell has excellent slotting lithium rejection ability and fires ability absolutely.
It is that the present invention has the utility model has the advantages that
(1) surface there is the magnesium alloy of micro-arc oxidation ceramic layer to be applied in lithium dynamical battery shell by the present invention, shell
Weight reduces about 60% relative to stainless steel case, effectively improves power battery energy density.
(2) for the present invention using potassium fluoride and sodium metasilicate as main salt, phosphate or carbonate are additive, citrate, boron
Hydrochlorate or tartrate are to carry out super differential arc oxidation to magnesium alloy using high frequency bidirectional pulse mode in the electrolyte of stabilizer,
The defects of ceramic membrane compactness of preparation is high, hole and crackle is few, and internal layer and the outer layer for realizing arc differential oxide ceramic coating are whole
Body densification.
(3) micro-arc oxidation ceramic layer even compact, wearability and corrosion resistance with higher solve in charge and discharge process
Electrolyte is to the etching problem of magnesium alloy, and effectively inhibits inducing capacity fading problem caused by inserting lithium phenomenon.
(4) super fine and close micro-arc oxidation films can effectively stop the oxygen transmission in combustion process, send out Mg alloy surface can only
Raw slowly oxidation thoroughly changes due to slow dysoxidation to provide the heat supply of magnesium alloy spontaneous combustion and thin-walled magnesium is inhibited to close
Gold causes the phenomenon that burning under high temperature or flame.
Detailed description of the invention
Fig. 1 is the diagrammatic cross-section after cylinder type lithium battery encapsulation, wherein 1 is the magnesium alloy with micro-arc oxidation ceramic layer
Shell, 2 be stainless steel negative electrode tab, and 3 be sealing ring.
Fig. 2 is A partial enlarged view in Fig. 1, and 11 be magnesium alloy substrate, and 12 be arc differential oxide ceramic coating.
Fig. 3 is the cyclic voltammetry curve comparison of exposed magnesium alloy shell and shell of the invention in electro-hydraulic in embodiment 1
Figure, wherein (A) figure is exposed magnesium alloy shell, (B) figure is shell of the invention.
Fig. 4 is the combustion experiment comparison diagram that magnesium alloy substrate (a) and the present invention prepare material (b) in embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
1. material prepares: after AZ31B magnesium alloy is smelted, being processed into billet.
2. shape extrusion: using 1000 tons of tube extruders, be processed into wall thickness 0.4mm through multi-pass hot extrusion, outside
Diameter is the magnesium alloy pipe of 18mm, is subsequently processed into the magnesium alloy shell base that length is 70mm.
3. surface treatment: by magnesium alloy shell base, after the pre-treatments such as mechanical grinding, chemical polishing, dipulse differential of the arc oxygen
Change technology carries out super arc differential oxide ceramic coating preparation, electrolyte: potassium fluoride 15g/L, sodium metasilicate 10g/L, phosphoric acid 5ml/L, just
Potassium phosphate sodium 10g/L, potassium tartrate 5g/L, remaining is water, pH=3.5；25 DEG C of temperature, micro-arc oxidation treatment 20min.Power supply mould
Formula: forward and reverse, positive end voltage is 500V, and negative sense end voltage is 30V, current density 2A/dm2, frequency 500Hz, positive and negative pulsewidth
Respectively 0.5ms and 0.2ms.1~2min is cleaned with tap water immediately after taking-up, then cleans 1~2min, this reality with deionized water
Applying an arc differential oxide ceramic coating layer thickness is about 20 μm.
4. stainless steel back cover: it is used as negative electrode tab using the stainless steel substrates with sealing ring, with a thickness of 0.5mm, progress slot rolling,
Back cover, edge sealing prepare lithium battery magnesium alloy shell, and structure is as shown in Figure 1,1 has micro-arc oxidation ceramic layer for surface
Magnesium alloy shell, 2 be stainless steel negative electrode tab, and 3 be sealing ring.The internal layer of the present embodiment shell is magnesium alloy substrate 11, and outer layer is
Arc differential oxide ceramic coating 12, as shown in Figure 2.
5. performance detection:
A, cyclic polarization is tested: in lithium battery electrolytes, by material manufactured in the present embodiment and stainless steel to electrode into
Row cyclic polarization test, cyclic voltammetry curve, which is shown, not to be occurred to insert lithium behavior, as shown in Fig. 3 (B)；With magnesium alloy substrate AZ31B
As control, as shown in Fig. 3 (A), there is obviously slotting lithium behavior；Prove that slotting lithium behavior can be effectively suppressed in material of the invention.
B, combustion experiment: material manufactured in the present embodiment being placed at 1000 DEG C and heats 5min, combustion phenomena does not occur, such as
Shown in Fig. 4 (b)；Using magnesium alloy substrate AZ31B as control, as shown in Fig. 4 (a), which burns immediately.Prove this hair
Bright material has anti-flammability.
Embodiment 2
1. material prepares: after AZ91B magnesium alloy is smelted, being processed into billet.
2. shape extrusion: using 1000 tons of tube extruders, be processed into wall thickness 0.4mm through multi-pass hot extrusion, outside
Diameter is the magnesium alloy pipe of 26mm, is subsequently processed into the magnesium alloy shell base that length is 70mm.
3. surface treatment: by magnesium alloy shell base, after the pre-treatments such as mechanical grinding, chemical polishing, dipulse differential of the arc oxygen
Change technology carries out super arc differential oxide ceramic coating preparation, electrolyte: potassium fluoride 20g/L, sodium metasilicate 15g/L, citric acid 5ml/L,
Sodium citrate 8g/L, sodium bicarbonate 10g/L, remaining is water, pH=9.0；25 DEG C of temperature, micro-arc oxidation treatment 20min, power supply mould
Formula: forward and reverse, positive end voltage is 750V, and negative sense end voltage is 40V, current density 2A/dm2, frequency 750Hz, positive and negative pulsewidth
Respectively 0.5ms and 0.3ms.1~2min is cleaned with tap water immediately after taking-up, then cleans 1~2min, this reality with deionized water
Applying an arc differential oxide ceramic coating layer thickness is about 25 μm.
4. stainless steel back cover: it is used as negative electrode tab using the stainless steel substrates with sealing ring, with a thickness of 0.5mm, progress slot rolling,
Back cover, edge sealing prepare lithium battery magnesium alloy shell.
5. performance detection: method inserts lithium phenomenon and dieseling hair without obvious with embodiment 1, material manufactured in the present embodiment
It is raw.
Embodiment 3
1. material prepares: after WE43 magnesium alloy is smelted, being processed into billet.
2. shape extrusion: using 1000 tons of tube extruders, be processed into wall thickness 0.4mm through multi-pass hot extrusion, outside
Diameter is the magnesium alloy pipe of 18mm, is subsequently processed into the magnesium alloy shell base that length is 70mm.
3. surface treatment: micro- using dipulse after the pre-treatments such as mechanical grinding, chemical polishing by magnesium alloy shell base
Arc oxidation technology carries out super arc differential oxide ceramic coating preparation, electrolyte: potassium fluoride 25g/L, sodium metasilicate 20g/L, hydrofluoric acid
5ml/L, sodium dihydrogen phosphate 8g/L, sodium tartrate 10g/L, remaining is water, pH=4.0；25 DEG C of temperature, micro-arc oxidation treatment
25min, electric source modes: forward and reverse, positive end voltage is 500V, and negative sense end voltage is 50V, current density 2.5A/dm2, frequency
750Hz, positive and negative pulsewidth are respectively 0.5ms and 0.5ms.1~2min is cleaned with tap water immediately after taking-up, then uses deionized water
1~2min is cleaned, the present embodiment arc differential oxide ceramic coating layer thickness is about 20 μm.
4. stainless steel back cover: it is used as negative electrode tab using the stainless steel substrates with sealing ring, with a thickness of 0.5mm, progress slot rolling,
Back cover, edge sealing prepare lithium battery magnesium alloy shell.
5. performance detection: method inserts lithium phenomenon and dieseling hair without obvious with embodiment 1, material manufactured in the present embodiment
It is raw.
Embodiment 4
1. material prepares: after WE94 magnesium alloy is smelted, being processed into billet.
2. shape extrusion: using 1000 tons of tube extruders, be processed into wall thickness 0.4mm through multi-pass hot extrusion, outside
Diameter is the magnesium alloy pipe of 26mm, is subsequently processed into the magnesium alloy shell base that length is 70mm.
3. surface treatment: micro- using dipulse after the pre-treatments such as mechanical grinding, chemical polishing by magnesium alloy shell base
Arc oxidation technology carries out super arc differential oxide ceramic coating preparation, electrolyte: potassium fluoride 30g/L, sodium metasilicate 20g/L, phosphoric acid 5ml/
L, potassium dihydrogen phosphate 10g/L, Boratex 10g/L, remaining is water, pH=3.8；25 DEG C of temperature, micro-arc oxidation treatment 20min, electricity
Source module: forward and reverse, positive end voltage is 800V, and negative sense end voltage is 35V, current density 2A/dm2, frequency 1000Hz, just,
Negative pulsewidth is respectively 0.5ms and 0.4ms.1~2min is cleaned with tap water immediately after taking-up, then 1 is cleaned with deionized water~
2min, the present embodiment arc differential oxide ceramic coating layer thickness are about 20 μm.
4. stainless steel back cover: it is used as negative electrode tab using the stainless steel substrates with sealing ring, with a thickness of 0.5mm, progress slot rolling,
Back cover, edge sealing prepare lithium battery magnesium alloy shell.
5. performance detection: method inserts lithium phenomenon and dieseling hair without obvious with embodiment 1, material manufactured in the present embodiment
It is raw.
The super ceramic coating formed by micro-arc oxidation of magnesium alloy prepared by above example, in the side such as anti-flammability and corrosion resistance, safety
Mask is greatly improved, while can satisfy the needs of lithium dynamical battery shell loss of weight.
Claims (4)
1. a kind of lithium ion battery, including shell, which is characterized in that the basis material of the shell is magnesium alloy, surface of shell
With micro-arc oxidation ceramic layer；
The micro-arc oxidation ceramic layer with a thickness of 5-40 μm, phase composition includes magnesium fluoride and trifluoro magnesium potassium；
The preparation method of the shell, comprising:
(1) magnesium alloy is processed into the casing of lithium ion battery base of cast；
(2) it by after the pretreatment of casing of lithium ion battery base, is placed in electrolyte and carries out micro-arc oxidation treatment, obtain surface with micro-
The casing of lithium ion battery of arc oxidation ceramic layer；
(3) stainless steel substrates back cover is used, lithium-ion battery shell is made；
The component of the electrolyte are as follows: potassium fluoride 10-40g/L, sodium metasilicate 10-50g/L, phosphate or sodium carbonate 5-20g/L, lemon
Lemon acid sodium, Boratex or tartrate 2-10g/L, remaining is water, pH value 3.5-9.0；
The condition of the micro-arc oxidation treatment: 15-50 DEG C of electrolyte temperature, oxidization time 20-45min；
The micro-arc oxidation treatment uses high frequency bidirectional pulse mode, frequency 100-1000Hz, current density 2-5A/dm2, just
It is 300-800V to whole voltage, negative sense end voltage is 30-80V, and positive duty ratio is 10%-50%, and negative sense duty ratio is 10%-
50%.
2. lithium ion battery as described in claim 1, which is characterized in that the component of the electrolyte are as follows: potassium fluoride 30g/L,
Sodium metasilicate 20g/L, phosphoric acid 5ml/L, potassium dihydrogen phosphate 10g/L, Boratex 10g/L, remaining is water, pH=3.8-4.0.
3. lithium ion battery as described in claim 1, which is characterized in that the condition of the micro-arc oxidation treatment: electrolyte temperature
25 DEG C of degree, oxidation processes 20min.
4. lithium ion battery as described in claim 1, which is characterized in that the micro-arc oxidation treatment uses high frequency bidirectional pulse
Mode, frequency 1000Hz, positive end voltage are 800V, and negative sense end voltage is 35V, current density 2A/dm2, positive and negative pulsewidth difference
For 0.5ms and 0.4ms.
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| CN106450096B (en) * | 2016-12-15 | 2019-03-19 | 衡阳市鑫晟新能源有限公司 | A kind of mobile phone heat dissipation lithium ion battery with aluminum shell |
| CN106848170B (en) * | 2017-03-24 | 2023-04-18 | 苏州景尊企业管理合伙企业(有限合伙) | Electrochemical device and method for manufacturing the same |
| CN109023481A (en) * | 2018-10-19 | 2018-12-18 | 北京杜尔考特科技有限公司 | Magnesium substrates production method, magnesium substrates with ceramic flame-proof layer and application thereof |
| CN118007216A (en) * | 2024-04-08 | 2024-05-10 | 上海航天精密机械研究所 | Micro-arc oxidation corrosion-resistant coating for rare earth magnesium alloy and preparation method thereof |
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| CN1747196A (en) * | 2004-09-08 | 2006-03-15 | 三星Sdi株式会社 | Lithium ion secondary battery |
| CN101365305A (en) * | 2007-08-07 | 2009-02-11 | 鸿富锦精密工业（深圳）有限公司 | Portable electronic device outer casing and manufacturing method thereof |
| CN102315395A (en) * | 2010-07-07 | 2012-01-11 | 上海航天电源技术有限责任公司 | Square lithium ion battery shell and square lithium ion power battery using same |
| CN202633393U (en) * | 2012-06-19 | 2012-12-26 | 深圳市科达利实业股份有限公司 | High-safety power cell shell |
| CN103789810A (en) * | 2014-01-15 | 2014-05-14 | 哈尔滨东安发动机（集团）有限公司 | Method for preparing micro-arc oxidation ceramic film layer on surface of magnesium alloy |
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| CN101098018A (en) * | 2006-06-30 | 2008-01-02 | 比亚迪股份有限公司 | Organic fuel cell |
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| CN1747196A (en) * | 2004-09-08 | 2006-03-15 | 三星Sdi株式会社 | Lithium ion secondary battery |
| CN101365305A (en) * | 2007-08-07 | 2009-02-11 | 鸿富锦精密工业（深圳）有限公司 | Portable electronic device outer casing and manufacturing method thereof |
| CN102315395A (en) * | 2010-07-07 | 2012-01-11 | 上海航天电源技术有限责任公司 | Square lithium ion battery shell and square lithium ion power battery using same |
| CN202633393U (en) * | 2012-06-19 | 2012-12-26 | 深圳市科达利实业股份有限公司 | High-safety power cell shell |
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