CN106025345A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
- Publication number
- CN106025345A CN106025345A CN201610524884.XA CN201610524884A CN106025345A CN 106025345 A CN106025345 A CN 106025345A CN 201610524884 A CN201610524884 A CN 201610524884A CN 106025345 A CN106025345 A CN 106025345A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- lithium ion
- shell
- magnesium alloy
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 61
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 239000010935 stainless steel Substances 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 12
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000011224 oxide ceramic Substances 0.000 claims description 21
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 21
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- 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
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 241001132374 Asta Species 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate 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
- 239000007788 liquid Substances 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
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 38
- 229910052744 lithium Inorganic materials 0.000 abstract description 38
- 239000000463 material Substances 0.000 abstract description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract 2
- 229910019400 Mg—Li Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 23
- 238000005524 ceramic coating Methods 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 241000357293 Leptobrama muelleri Species 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 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
- 238000002474 experimental method Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000001192 hot extrusion Methods 0.000 description 4
- 239000012528 membrane Substances 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
- 230000002269 spontaneous effect Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 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
- ASHGTUMKRVIOLH-UHFFFAOYSA-L potassium;sodium;hydrogen phosphate Chemical compound [Na+].[K+].OP([O-])([O-])=O ASHGTUMKRVIOLH-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- 206010011376 Crepitations Diseases 0.000 description 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 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 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
- 150000004673 fluoride salts Chemical group 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
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 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
- 230000001590 oxidative 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
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 239000003381 stabilizer Substances 0.000 description 1
- 229940095064 tartrate Drugs 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 lithium ion battery, and belongs to the field of material preparation. The lithium ion battery comprises a shell, a base material of the shell is magnesium alloy, and the surface of the shell is provided with a micro-arc oxidized ceramic layer; the thickness of the micro-arc oxidized ceramic layer is 5 micrometers to 40 micrometers, and the phase composition mainly comprises magnesium fluoride, trifluoro-magnesium potassium and a small amount of magnesium oxide, wherein the PBR of magnesium fluoride is larger than 1. The invention further discloses a preparation method of the battery shell. According to the lithium ion battery, magnesium alloy of which the surface is provided with the micro-arc oxidized ceramic layer is applied to the lithium-ion power battery shell, and therefore the mass of the prepared battery shell is decreased by about 60% relative to a stainless steel shell; the battery shell does not spontaneously burn if the battery shell burns within 5 minutes at 1,000 DEG C; through 1,000 times of circulating charge and discharge testing, no obvious lithium inserting phenomenon is generated in a Mg-Li electric pair.
Description
Technical field
The present invention relates to field of material preparation, be specifically related to a kind of lithium ion battery.
Background technology
Lithium dynamical battery has running voltage height, has extended cycle life, and the feature that specific energy is high obtains extensively in new-energy automobile field
General application.Although lithium dynamical battery energy density has been greatly improved, but still it is difficult to meet consumer to power vapour
Car course continuation mileage demand.Current battery technological design relative maturity, with LiFePO4 and ternary material as positive pole, material with carbon element be
The lithium-ion-power cell of negative pole is difficult to there is big breakthrough in energy density, therefore, finds new way and promotes lithium dynamical battery
Energy density is imperative.
Lithium dynamical battery typically uses stainless steel material to make battery case, and the 1/4～1/3 of Stainless Steel Shell battery core to be accounted for gross weight
Left and right, uses light alloy material to substitute rustless steel and alleviates the weight of battery case, be improve electrokinetic cell energy density one
Effective means.Aluminium alloy is the light alloy material more commonly used, and there is data to suggest that the aluminum hull material weight of same model electrokinetic cell relatively
Stainless steel case material want light more than half, additionally, due to aluminum hull material hardness is less, when cell internal pressure is bigger, hold very much
Easily being released by aluminium shell, aluminum hull is more sharp for inner pressure of battery reaction, and the internal pressure of box hat alloy is anti-by contrast
Should be blunt, therefore, use aluminium shell material can increase substantially the safety of electrokinetic cell.But, aluminum hull easily corrodes,
Once the performance of battery and safety will be negatively affected by housing corrosion, and process for treating surface (plating commonly used by aluminum current alloy
Nickel, differential arc oxidation etc.), the needs of industrialized production no matter still it are unable to reach from technology maturity or scale cost control.
Magnesium is one of the lightest metal, and its relative density only has 1.74g/cm3, about the 2/3 of aluminum, the 1/4 of ferrum, have good
Characteristic is reclaimed in damping property, heat conductivity, electromagnetic wave shielding, machining property and reprocessing.Therefore, magnesium alloy is used to substitute
Lithium dynamical battery stainless steel casing, and then promote battery specific energy, extend the course continuation mileage of power car.If directly using magnesium to close
Gold does lithium dynamical battery shell, and after negative pole UNICOM, magnesium sheath voltage is 0.3V (vs.Li+/ Li) near time, exist and significantly insert
Lithium behavior, not only can make charge efficiency reduce and battery electrochemical capacity loss, also can corrode magnesium alloy case simultaneously；It addition,
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, as
Really lithium battery meets with and destroys, extrudes, burns when puncturing, easily cause the spontaneous combustion of magnesium alloy shell, and then it is electric to aggravate lithium
Combustion explosion, brings great hidden danger to the safety of electrokinetic cell.
As can be seen here, using magnesium alloy must first have to solve magnesium alloy as lithium dynamical battery occurs slotting lithium behavior to damage with electrolyte
Power consumption chemical capacity problem, stops lithium battery destruction burning and causes the potential safety hazard of magnesium alloy spontaneous combustion.The most not yet it is found to full
The solution of foot requirements above.
Summary of the invention
The invention provides a kind of lithium ion battery, processing, at magnesium alloy by magnesium alloy shell being carried out super fine and close differential arc oxidation
Surface forms one layer of even compact oxidation ceramic layer, overcomes magnesium alloy to be directly used as the slotting lithium problem that lithium dynamical battery shell exists,
Meet lithium battery loss of weight, the demand of safety simultaneously.
A kind of lithium ion battery, including housing, the matrix material of described housing is magnesium alloy, and surface of shell has differential arc oxidation pottery
Enamel coating.
The thickness of described arc differential oxide ceramic layer is 5-40 μm, and phase composition mainly includes Afluon (Asta) and trifluoro magnesium potassium, its PBR ＞ 1,
And a small amount of magnesium oxide.
The present invention is by adjusting Microarc oxidation electrolyte formula so that the main phase composition of arc differential oxide ceramic layer is fluoride, replaces
Traditional magnesia ceramics coating.The main component Afluon (Asta) of film layer not only PBR ＞ 1 so that ceramic membrane compactness is high, hole
Few with defects such as crackles, completely cut off the diffusive migration of electrolyte, and the crystal structure of ceramic membrane has made lithium ion to embed, from
And effectively suppress to insert the generation of lithium behavior.Additionally, this film layer has higher chemical stability, even if lithium electricity matter occurs a small amount of
Water suction is decomposed, and also will not cause film layer corrosion failure, ensures the inhibitory action to slotting lithium behavior under actual environment.
Burn test results shows, the magnesium alloy with arc differential oxide ceramic layer of the present invention possesses anti-flammability and (heats 5 at 1000 DEG C
Min is reactionless).Therefore, this material, as battery container, will not occur to cause transient temperature rising to cause shell because battery goes to pot
The situation of body spontaneous combustion, meets the requirement of lithium dynamical battery safety.
It is it addition, the battery container of the present invention is because arc differential oxide ceramic coating uniform is fine and close, flat smooth, good with basal body binding force,
Having higher wearability, solve the electrolyte etching problem to magnesium alloy in charge and discharge process, lithium phenomenon is inserted in suppression.Charge and discharge
Electricity test result indicate that, the battery container of the present invention occurs without the most slotting lithium phenomenon after 1000 cycle charge-discharges of experience.
The preparation method of described housing, including:
(1) magnesium alloy is processed into the casing of lithium ion battery base of cast；
(2) by after casing of lithium ion battery base pretreatment, it is placed in electrolyte and carries out differential arc oxidation process, surface must be arrived and have micro-
The casing of lithium ion battery of arc oxidation ceramic layer；
(3) use stainless steel substrates back cover, prepare lithium-ion battery shell.
In battery container of the present invention preparation, first carry out magnesium alloy shell processing and forming, then carry out mechanical grinding, chemical polishing etc.
Pretreatment, then uses differential arc oxidation to process on magnesium alloy shell surface and forms differential arc oxidation compactness ceramic coating, finally carry out
Rustless steel back cover.
Described magnesium alloy is AZ31B, AZ91B, WE43 or WE94, and raw material magnesium alloy is through multi-pass extruding or punching press, system
For going out magnesium alloy thin-wall pipe, tube wall thickness is 0.4-5mm, and external diameter is 10-100mm, the most as required by tubular object extruding
Become the battery case base of corresponding size.
The component of described electrolyte is: potassium fluoride 10-40g/L, sodium silicate 10-50g/L, phosphate or sodium carbonate 5-20g/L,
Sodium citrate, sodium borate or tartrate 2-10g/L, remaining is water, and pH value is 3.5-9.0.
Potassium fluoride provides the fluorion in electrolyte, and its concentration determines the content of Afluon (Asta) in ceramic coating formed by micro-arc oxidation, adjusts concentration
Change from 10g/L to 40g/L, reach maximum when concentration reaches 30g/L, improve further with concentration, film layer Afluon (Asta)
Content is held essentially constant.
Described phosphate is potassium orthophosphate, potassium orthophosphate sodium, potassium phosphate,monobasic, disodium-hydrogen, potassium dihydrogen phosphate, di(2-ethylhexyl)phosphate
The mixture of one or more in hydrogen sodium, PTPP (potassium tripolyphosphate) or sodium tripolyphosphate；Carbonate is sodium carbonate or sodium bicarbonate；Winestone
Hydrochlorate is Soluble tartar. or sodium potassium tartrate tetrahydrate.The above-mentioned additive for electrolyte, affects the oxidizing process of differential arc oxidation, to oxidation
The compactness of film has decisive action, adjusts the concentration of additive, can improve the compactness of film layer.
As preferably, the component of described electrolyte is: potassium fluoride 30g/L, sodium silicate 20g/L, phosphoric acid 5ml/L, di(2-ethylhexyl)phosphate
Hydrogen potassium 10g/L, sodium borate 10g/L, remaining is water, pH=3.8-4.0.
Described differential arc oxidation processes and uses high frequency bidirectional pulse mode, and frequency is 100-1000Hz, electric current density 2-5A/dm2, just
Being 300-800V to whole voltage, negative sense voltage at end is 30-80V, and forward dutycycle is 10%-50%, and negative sense dutycycle is
10%-50%.The high-frequency impulse used has densification, and the micro-arc oxidation films prepared by adjustment electrical quantity is uniform, cause
Density is high.
As preferably, frequency is 1000Hz, and forward voltage at end is 800V, and negative sense voltage at end is 35V, and electric current density is 2A/dm2,
Positive and negative pulsewidth is respectively 0.5ms and 0.4ms.
The condition that described differential arc oxidation processes: electrolyte temperature 15-50 DEG C, oxidization time is 20-45min.
Adjust electric current density from 2A/dm2To 5A/dm2, the growth rate of film layer can be improved, electric current density is the biggest, and film layer is raw
Long the fastest.Oxidization time is 20-45min, and along with the prolongation of oxidization time, thicknesses of layers increases, by adjusting oxidization time,
The thicknesses of layers scope ceramic membrane in 5-40 μm can be obtained.As preferably, electrolyte temperature 25 DEG C, oxidation processes 20min.
By above-mentioned electrolyte and the adjustment of electrical quantity, the super fine and close ceramic film of final acquisition, make magnesium alloy housing of power cell
There is the slotting lithium rejection ability of excellence and exhausted combustion ability.
The beneficial effect that the present invention possesses:
(1) surface is had the magnesium alloy of arc differential oxide ceramic layer and is applied in lithium dynamical battery housing by the present invention, its housing quality
Reduce relative to stainless steel case and be about 60%, be effectively improved electrokinetic cell energy density.
(2) present invention with potassium fluoride and sodium silicate be main salt, phosphate or carbonate for additive, citrate, borate
Or in the electrolyte that tartrate is stabilizer, use high frequency bidirectional pulse mode that magnesium alloy is carried out super differential arc oxidation, preparation
Ceramic membrane compactness is high, and the defect such as hole and crackle is few, it is achieved that the internal layer of arc differential oxide ceramic coating and outer layer entirety densification.
(3) arc differential oxide ceramic layer even compact, has higher wearability and corrosion resistance, solves to be electrolysed in charge and discharge process
The liquid etching problem to magnesium alloy, and effectively the inducing capacity fading problem that lithium phenomenon causes is inserted in suppression.
(4) super fine and close micro-arc oxidation films can effectively stop the oxygen transmission in combustion process, makes Mg alloy surface can only occur slowly
Oxidation, owing to slow dysoxidation is to provide the heat supply of magnesium alloy spontaneous combustion, thoroughly changes and inhibits thin-wall Mg alloy at high temperature
Or under flame, cause the phenomenon of burning.
Accompanying drawing explanation
Fig. 1 is the generalized section after cylinder type lithium battery encapsulation, and wherein 1 is the magnesium alloy shell with arc differential oxide ceramic layer,
2 is rustless steel negative plate, and 3 is sealing ring.
Fig. 2 is A partial enlarged drawing in Fig. 1, and 11 is magnesium alloy substrate, and 12 is arc differential oxide ceramic coating.
Fig. 3 is the housing of exposed magnesium alloy shell and present invention cyclic voltammetry curve comparison diagram in electro-hydraulic in embodiment 1, its
In (A) figure be exposed magnesium alloy shell, (B) figure is the housing of the present invention.
Fig. 4 is the combustion experiment comparison diagram that in embodiment 1, magnesium alloy substrate (a) and the present invention prepare material (b).
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
1. material prepares: after AZ31B magnesium alloy is smelted, be processed into billet.
2. shape extrusion: use 1000 tons of tube extruders, be processed into wall thickness 0.4mm, external diameter through multi-pass hot extrusion
For the magnesium alloy pipe of 18mm, it is subsequently processed into the magnesium alloy shell base of a length of 70mm.
3. surface processes: by magnesium alloy shell base, after the pre-treatment such as mechanical grinding, chemical polishing, dipulse differential arc oxidation skill
Art carries out super arc differential oxide ceramic coating and prepares, electrolyte: potassium fluoride 15g/L, sodium silicate 10g/L, phosphoric acid 5ml/L, just
Potassium phosphate sodium 10g/L, Soluble tartar. 5g/L, remaining is water, pH=3.5；Temperature 25 DEG C, differential arc oxidation processes 20min.
Electric source modes: forward and reverse, forward voltage at end is 500V, and negative sense voltage at end is 30V, electric current density 2A/dm2, frequency 500
Hz, positive and negative pulsewidth is respectively 0.5ms and 0.2ms.Clean 1～2min with tap water immediately after taking-up, then use deionized water
Cleaning 1～2min, the present embodiment arc differential oxide ceramic coating layer thickness is about 20 μm.
4. rustless steel back cover: using and have the stainless steel substrates of sealing ring as negative plate, thickness is 0.5mm, carries out slot rolling, envelope
The end, edge sealing, prepare lithium battery magnesium alloy shell, and its structure is as it is shown in figure 1,1 has arc differential oxide ceramic layer for surface
Magnesium alloy shell, 2 is rustless steel negative plate, and 3 is sealing ring.The internal layer of the present embodiment housing is magnesium alloy substrate 11, outer layer
For arc differential oxide ceramic coating 12, as shown in Figure 2.
5. performance detection:
A, cyclic polarization experiment: in lithium battery electrolytes, electrode is circulated by the material prepared by the present embodiment with rustless steel
Polarization test, cyclic voltammetry curve show and slotting lithium behavior does not occurs, as shown in Fig. 3 (B)；Using magnesium alloy substrate AZ31B as right
According to, as shown in Fig. 3 (A), there is lithium behavior of substantially inserting；Prove that the material of the present invention can effectively suppress to insert lithium behavior.
B, combustion experiment: the material prepared by the present embodiment is placed at 1000 DEG C heating 5min, and combustion phenomena does not occurs, as
Shown in Fig. 4 (b)；Using magnesium alloy substrate AZ31B as comparison, as shown in Fig. 4 (a), this base material burns immediately.Prove this
The material of invention has anti-flammability.
Embodiment 2
1. material prepares: after AZ91B magnesium alloy is smelted, be processed into billet.
2. shape extrusion: use 1000 tons of tube extruders, be processed into wall thickness 0.4mm, external diameter through multi-pass hot extrusion
For the magnesium alloy pipe of 26mm, it is subsequently processed into the magnesium alloy shell base of a length of 70mm.
3. surface processes: by magnesium alloy shell base, after the pre-treatment such as mechanical grinding, chemical polishing, dipulse differential arc oxidation skill
Art carries out super arc differential oxide ceramic coating and prepares, electrolyte: potassium fluoride 20g/L, sodium silicate 15g/L, citric acid 5ml/L,
Sodium citrate 8g/L, sodium bicarbonate 10g/L, remaining is water, pH=9.0；Temperature 25 DEG C, differential arc oxidation processes 20min,
Electric source modes: forward and reverse, forward voltage at end is 750V, and negative sense voltage at end is 40V, electric current density 2A/dm2, frequency 750
Hz, positive and negative pulsewidth is respectively 0.5ms and 0.3ms.Clean 1～2min with tap water immediately after taking-up, then use deionized water
Cleaning 1～2min, the present embodiment arc differential oxide ceramic coating layer thickness is about 25 μm.
4. rustless steel back cover: using and have the stainless steel substrates of sealing ring as negative plate, thickness is 0.5mm, carries out slot rolling, envelope
The end, edge sealing, prepare lithium battery magnesium alloy shell.
5. performance detection: method is with embodiment 1, and material prepared by the present embodiment occurs without substantially inserting lithium phenomenon and dieseling.
Embodiment 3
1. material prepares: after WE43 magnesium alloy is smelted, be processed into billet.
2. shape extrusion: use 1000 tons of tube extruders, be processed into wall thickness 0.4mm, external diameter through multi-pass hot extrusion
For the magnesium alloy pipe of 18mm, it is subsequently processed into the magnesium alloy shell base of a length of 70mm.
3. surface processes: by magnesium alloy shell base, after the pre-treatment such as mechanical grinding, chemical polishing, uses dipulse differential of the arc oxygen
Change technology carries out super arc differential oxide ceramic coating and prepares, electrolyte: potassium fluoride 25g/L, sodium silicate 20g/L, Fluohydric acid. 5ml/L,
Sodium dihydrogen phosphate 8g/L, sodium tartrate 10g/L, remaining is water, pH=4.0；Temperature 25 DEG C, differential arc oxidation processes 25min,
Electric source modes: forward and reverse, forward voltage at end is 500V, and negative sense voltage at end is 50V, electric current density 2.5A/dm2, frequency 750
Hz, positive and negative pulsewidth is respectively 0.5ms and 0.5ms.Clean 1～2min with tap water immediately after taking-up, then use deionized water
Cleaning 1～2min, the present embodiment arc differential oxide ceramic coating layer thickness is about 20 μm.
4. rustless steel back cover: using the stainless steel substrates with sealing ring as negative plate, thickness is 0.5mm, carries out slot rolling, envelope
The end, edge sealing, prepare lithium battery magnesium alloy shell.
5. performance detection: method is with embodiment 1, and material prepared by the present embodiment occurs without substantially inserting lithium phenomenon and dieseling.
Embodiment 4
1. material prepares: after WE94 magnesium alloy is smelted, be processed into billet.
2. shape extrusion: use 1000 tons of tube extruders, be processed into wall thickness 0.4mm, external diameter through multi-pass hot extrusion
For the magnesium alloy pipe of 26mm, it is subsequently processed into the magnesium alloy shell base of a length of 70mm.
3. surface processes: by magnesium alloy shell base, after the pre-treatment such as mechanical grinding, chemical polishing, uses dipulse differential of the arc oxygen
Change technology carries out super arc differential oxide ceramic coating and prepares, electrolyte: potassium fluoride 30g/L, sodium silicate 20g/L, phosphoric acid 5ml/L,
Potassium dihydrogen phosphate 10g/L, sodium borate 10g/L, remaining is water, pH=3.8；Temperature 25 DEG C, differential arc oxidation processes 20min,
Electric source modes: forward and reverse, forward voltage at end is 800V, and negative sense voltage at end is 35V, electric current density 2A/dm2, frequency 1000
Hz, positive and negative pulsewidth is respectively 0.5ms and 0.4ms.Clean 1～2min with tap water immediately after taking-up, then use deionized water
Cleaning 1～2min, the present embodiment arc differential oxide ceramic coating layer thickness is about 20 μm.
4. rustless steel back cover: using and have the stainless steel substrates of sealing ring as negative plate, thickness is 0.5mm, carries out slot rolling, envelope
The end, edge sealing, prepare lithium battery magnesium alloy shell.
5. performance detection: method is with embodiment 1, and material prepared by the present embodiment occurs without substantially inserting lithium phenomenon and dieseling.
Magnesium alloy prepared by above example surpasses ceramic coating formed by micro-arc oxidation, has in anti-flammability and the aspect such as corrosion resistance, safety
Bigger raising, disclosure satisfy that the needs of lithium dynamical battery housing loss of weight simultaneously.
Claims (9)
1. a lithium ion battery, including housing, it is characterised in that the matrix material of described housing is magnesium alloy, surface of shell
There is arc differential oxide ceramic layer.
2. lithium ion battery as claimed in claim 1, it is characterised in that the thickness of described arc differential oxide ceramic layer is 5-40 μm,
Phase composition includes Afluon (Asta) and trifluoro magnesium potassium.
3. lithium ion battery as claimed in claim 1, it is characterised in that the preparation method of described housing, including:
(1) magnesium alloy is processed into the casing of lithium ion battery base of cast；
(2) by after casing of lithium ion battery base pretreatment, it is placed in electrolyte and carries out differential arc oxidation process, surface must be arrived and have micro-
The casing of lithium ion battery of arc oxidation ceramic layer；
(3) use stainless steel substrates back cover, prepare lithium-ion battery shell.
4. lithium ion battery as claimed in claim 3, it is characterised in that the component of described electrolyte is: potassium fluoride 10-40g/L,
Sodium silicate 10-50g/L, phosphate or sodium carbonate 5-20g/L, sodium citrate, sodium borate or tartrate 2-10g/L, remaining
For water, pH value is 3.5-9.0.
5. lithium ion battery as claimed in claim 4, it is characterised in that the component of described electrolyte is: potassium fluoride 30g/L,
Sodium silicate 20g/L, phosphoric acid 5ml/L, potassium dihydrogen phosphate 10g/L, sodium borate 10g/L, remaining is water, pH=3.8-4.0.
6. lithium ion battery as claimed in claim 3, it is characterised in that the condition that described differential arc oxidation processes: electrolysis liquid temperature
Spending 15-50 DEG C, oxidization time is 20-45min.
7. lithium ion battery as claimed in claim 6, it is characterised in that the condition that described differential arc oxidation processes: electrolysis liquid temperature
Spend 25 DEG C, oxidation processes 20min.
8. lithium ion battery as claimed in claim 3, it is characterised in that described differential arc oxidation processes and uses high frequency bidirectional pulse
Mode, frequency is 100-1000Hz, electric current density 2-5A/dm2, forward voltage at end is 300-800V, and negative sense voltage at end is 30-80
V, forward dutycycle is 10%-50%, and negative sense dutycycle is 10%-50%.
9. lithium ion battery as claimed in claim 8, it is characterised in that described differential arc oxidation processes and uses high frequency bidirectional pulse
Mode, frequency 1000Hz, forward voltage at end is 800V, and negative sense voltage at end is 35V, electric current density 2A/dm2, positive and negative
Pulsewidth is respectively 0.5ms and 0.4ms.
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| 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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