CN107799767B - Iodide soft package battery and assembling method thereof - Google Patents
Iodide soft package battery and assembling method thereof Download PDFInfo
- Publication number
- CN107799767B CN107799767B CN201610794081.6A CN201610794081A CN107799767B CN 107799767 B CN107799767 B CN 107799767B CN 201610794081 A CN201610794081 A CN 201610794081A CN 107799767 B CN107799767 B CN 107799767B
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- battery
- iodide
- aluminum
- carbon
- ion
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 43
- 150000003839 salts Chemical class 0.000 claims abstract description 37
- 239000002985 plastic film Substances 0.000 claims abstract description 36
- 229920006255 plastic film Polymers 0.000 claims abstract description 36
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011630 iodine Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 112
- -1 imidazolium ions Chemical class 0.000 claims description 58
- 229910052782 aluminium Inorganic materials 0.000 claims description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 17
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000002608 ionic liquid Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 13
- 150000002892 organic cations Chemical class 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 238000003475 lamination Methods 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000010309 melting process Methods 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 238000009517 secondary packaging Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 5
- 238000004080 punching Methods 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 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 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
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- 229910052731 fluorine Inorganic materials 0.000 claims description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
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- 238000001291 vacuum drying Methods 0.000 claims description 4
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical group Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001913 cellulose Substances 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 18
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- 238000001816 cooling Methods 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 12
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- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- IFERXQKQRBVNKP-UHFFFAOYSA-K tetraethylazanium triiodide Chemical compound [I-].[I-].[I-].CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC IFERXQKQRBVNKP-UHFFFAOYSA-K 0.000 description 6
- HGQMFMRIAHRFNZ-UHFFFAOYSA-N CCN1C=CN(C)C1.I.I.I Chemical compound CCN1C=CN(C)C1.I.I.I HGQMFMRIAHRFNZ-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- COELWDHEVBNFLF-UHFFFAOYSA-N 1-ethyl-3-methyl-2H-imidazole hydroiodide Chemical compound I.CCN1CN(C)C=C1 COELWDHEVBNFLF-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
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- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 3
- RMGORBUEQQOJMG-UHFFFAOYSA-N CCN1C=CC=CC1.I.I.I Chemical group CCN1C=CC=CC1.I.I.I RMGORBUEQQOJMG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- AVJBQMXODCVJCJ-UHFFFAOYSA-M 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-1-ium;chloride Chemical class [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C=[N+](C=2C(=CC=CC=2C(C)C)C(C)C)C=C1 AVJBQMXODCVJCJ-UHFFFAOYSA-M 0.000 description 1
- OOAKIOMAIRZQKN-UHFFFAOYSA-M 1-butyl-1-methylpiperidin-1-ium;iodide Chemical compound [I-].CCCC[N+]1(C)CCCCC1 OOAKIOMAIRZQKN-UHFFFAOYSA-M 0.000 description 1
- VWYWWUCXQMXQGF-UHFFFAOYSA-N 1-ethyl-2,4,5-triiodo-3-methyl-2H-imidazole Chemical compound C(C)N1C(N(C(=C1I)I)C)I VWYWWUCXQMXQGF-UHFFFAOYSA-N 0.000 description 1
- XVQLCOQENXWRQC-UHFFFAOYSA-N 1-ethyl-3-methylimidazol-3-ium triiodide Chemical compound [I-](I)I.C(C)[N+]1=CN(C=C1)C XVQLCOQENXWRQC-UHFFFAOYSA-N 0.000 description 1
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- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
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- SBSSZSCMFDYICE-UHFFFAOYSA-N tetrabutylazanium;triiodide Chemical compound I[I-]I.CCCC[N+](CCCC)(CCCC)CCCC SBSSZSCMFDYICE-UHFFFAOYSA-N 0.000 description 1
- KZLXBZDNRACERI-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC KZLXBZDNRACERI-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0404—Machines for assembling batteries
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to an iodide soft package battery and an assembling method thereof, wherein the battery comprises: the battery comprises a battery pole group, a positive pole tab, a negative pole tab, electrolyte and an aluminum-plastic film; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the anode comprises an anode current collector and an iodide anode component coated on the surface of the anode current collector; the positive active substance in the iodide positive electrode component is iodide, and the iodide is obtained by reacting an iodine simple substance with organic salt. The invention adopts the iodide generated by the reaction of the iodine simple substance and the organic salt as the positive active substance, and when the iodide is used for the battery, the specific energy of the secondary battery can be greatly improved, and the quick charge and discharge can be realized, the cycle life is long, and the cost of raw materials is low.
Description
Technical Field
The invention relates to the field of secondary batteries, in particular to a battery and an assembling method thereof, and particularly relates to an iodide soft package battery and an assembling method thereof.
Background
At present, the battery is the heart of the electric automobile and is the current investment hotspot, and the lithium ion power battery is considered as the power battery with the most development potential of the electric automobile; however, with the development of noble metals such as nickel, cobalt, lithium and the like, the raw materials of the lithium ion power battery greatly increase, and the popularization and the application of the electric automobile are restricted; the poor safety and the poor recovery economic benefit of the lithium ion power battery are also important factors restricting the development of the lithium ion power battery. The power battery solution with low cost, environmental protection and safe use is still the first problem to be solved by the electric automobile.
Halogen is an element which is stored in the earth crust abundantly, and has the advantages of large storage capacity, mature extraction process, environmental protection in production, no pollution in recovery and low price, and the halogen is taken as the anode material and is an ideal electrode material.
Disclosure of Invention
In order to solve the technical problems, the inventor of the present invention found through research that when an iodide generated by reacting a simple substance of iodine with an organic salt is used as a positive electrode active material in a battery, a power battery with low cost, environmental protection, safe use and high specific energy can be obtained, thereby achieving the present invention.
In a first aspect, the present invention provides an iodide pouch battery comprising: the battery comprises a battery pole group, a positive pole tab, a negative pole tab, electrolyte and an aluminum-plastic film; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the positive electrode comprises a positive electrode current collector and an iodide positive electrode component coated on the surface of the positive electrode current collector.
The term "comprising" as used herein means that it may include other components in addition to the components described, which impart different characteristics to the battery. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
According to the present invention, the iodide cathode composition comprises: iodide, high surface area activated carbon, conductive agent and binder, and may also include other components known in the art.
The iodide anode comprises the following components in parts by weight:
the positive electrode containing the iodide positive electrode component of the present invention may be prepared by the following method, but is not limited thereto:
(1) putting iodide, high specific surface area activated carbon, a conductive agent and a binder into a ball milling tank, and carrying out ball milling for 5-120 min;
(2) adding an organic solvent into a ball milling tank, enabling the mass ratio of the total mass of the iodide, the high specific surface area activated carbon, the conductive agent and the binder to the organic solvent to be (40-60) - (60-40), and carrying out ball milling for 60-120min to obtain anode slurry;
(3) coating the positive electrode slurry on a current collector, and controlling the coating thickness of one side to be 100-300 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and performing vacuum baking, wherein the vacuum degree is controlled to be-0.08 to-0.10 MPa, the temperature is controlled to be 100-;
(5) and extruding the dried pole piece by using a double-roller machine, and controlling the pressure of the double rollers to be 50-300 tons to obtain the anode containing the iodide anode component.
Wherein the iodide is 20-97 parts by weight of the iodide cathode component, such as 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 50 parts, 55 parts, 60 parts, 63 parts, 68 parts, 70 parts, 75 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts or 97 parts, and the specific values therebetween are limited to space and for brevity, and the invention is not exhaustive.
According to the present invention, the positive active material iodide is obtained by reacting iodonium (elemental iodine) with an organic salt.
The iodide provided by the invention is used as a novel chemical system and exists in the positive active material of the battery in a liquid form. By adding the iodide into the positive active material, the theoretical specific energy of the positive active material can reach as high as 211mAh/g, so that the prepared secondary battery has higher specific energy, rapid charge and discharge are realized, the cycle life is prolonged, and the cost of raw materials is low.
According to the invention, the organic salt has the general formula [ X ]]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion.
The organic salt is composed of organic cations with larger volume and anions with smaller volume, and the substance has a plurality of unique properties, such as stable physicochemical properties, extremely low vapor pressure and difficult volatilization, good solubility to both organic and inorganic substances, controllable polarity and the like.
In the present invention, the organic cation may be any one of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium ion or quaternary phosphonium ion or a combination of at least two thereof, for example, may be any one of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium ion or quaternary phosphonium ion, and a typical but non-limiting combination is: imidazolium ions and pyridinium ions; pyridinium ions and pyrrolium ions; morpholinium ions, quaternary ammonium ions, quaternary phosphonium ions and the like.
According to the invention, the organic cation is preferably a quaternary ammonium ion, which has the following advantages over other organic cations: the quaternary ammonium salt (organic salt containing quaternary ammonium salt ions) is a common chemical, and the production process is mature, the price is low, and the quaternary ammonium salt can be purchased and used in a large scale.
In the present invention, the anion may adopt F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them, for example, may be F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3S02)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -A typical but non-limiting combination of any of: f-And Cl-;Br-And I-;I-And PF6 -;Cl-、Br-And SCN-And the like.
Illustratively, the organic salt in the present invention may be: 1-butyl-3-methylimidazolium hexafluorophosphate ([ C)4-min]PF4)1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride salt, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 1-N-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-propylimidazolium iodide, cetylpyridinium chloride, pyridinium triiodide, N-allyl-2-alkylpyridinium chloride salt, 1-butyl-1-methylpiperidinium iodide, chlorodipiperidinium hexafluorophosphate, cetyltrimethylammonium chloride, tetramethylammonium chloride, ethyltriphenylphosphonium iodide, hexadecyltributylphosphonium iodide, and the like.
By using the iodide as the active material of the positive electrode, the prepared secondary battery has higher specific energy, and the low cost, environmental protection and safe use of the power battery can be realized.
According to the invention, the iodide is obtained by reacting elementary iodine with the above-mentioned organic salt [ X ]]+Z-The chemical reaction of the compound prepared by the reaction of mixing can be expressed by the following equation:
4I2+[X]+Z-→[X]+[I8Z]-or I2+[X]+Z-→[X]+[I2Z]-
In this chemical reaction, 1 [ X ]]+Z-Molecules which can complex up to 4I2The molar ratio of iodine to organic salt can thus be set in the range of (1-4): 1.
In the invention, the iodide is added into the positive electrode active material, so that the capacitor can have higher specific energy, and the theoretical specific energy of the iodide is up to 211 mAh/g.
Illustratively, in the present invention, the iodide may be: tetraethylammonium triiodide, tetrabutylammonium triiodide, 1-ethyl-3-methyl-triiodoimidazole, phenyltrimethylammonium triiodide, benzyltriethylammonium triiodide, benzyltrimethylammonium triiodide, dodecyltrimethylammonium triiodide.
The iodide in the present invention can be prepared by the following method, but is not limited thereto:
(a) respectively taking an iodine simple substance and organic salt, controlling the molar ratio of the iodine simple substance to the organic salt to be (1-4):1, firstly putting the organic salt into a closed container, and introducing inert gas into the closed container, wherein the inert gas is preferably nitrogen and/or argon;
(b) adding iodine into a closed container, controlling the whole process to be 1-60min, stirring and cooling in the adding process, and controlling the temperature to be within 50 ℃;
(c) and after the iodine simple substance is added, cooling to room temperature to obtain the iodide.
According to the present invention, the iodide is preferably prepared by the above method, which has the following advantages: the method can be completed in a closed reaction container at one time by one-time feeding without processes of purification, evaporation, filtration and the like, and the production period can be shortened to within 1 hour.
In the preparation process of the iodide in the present invention, the molar ratio of the iodine element in the step (a) to the organic salt is (1-4):1, for example, 1:1, 2:1, 3:1 or 4:1, and specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive list of the specific values included in the range.
In the process for preparing iodide in the present invention, the closed container in step (a) may be a closed container known in the art, for example, an autoclave, which is not particularly limited herein. In the closed container, an inert gas must be introduced, and the inert gas can be an inert gas commonly used in the art, such as nitrogen, argon, helium, etc., preferably nitrogen, argon or a mixture thereof.
In the preparation process of the iodide in the present invention, the time for controlling the whole reaction process in step (b) is 1-60min, for example, 1min, 5min, 10min, 12min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, and the specific values between the above values are limited by space and for the sake of brevity, and the present invention is not exhaustive of the specific values included in the range; the reaction temperature is controlled within 50 ℃ to prevent the iodine simple substance from volatilizing and ensure the full reaction of the iodine simple substance and the organic salt.
According to the present invention, the high specific surface area activated carbon is present in the iodide cathode component in an amount of 1 to 50 parts by weight, for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts or 50 parts by weight, and specific values therebetween are not limited to space and for brevity, and the present invention is not exhaustive.
The term "high specific surface area activated carbon" in the present invention means that the specific surface area is 1000-2The iodine value of the activated carbon per gram is more than 1500mg/g, and the specific meeting indexes are shown in the table.
Specific surface area (m)2/g) | 1000-3500 | Iodine value (mg/g) | >1500 |
Moisture (%) | <0.1 | Ash (%) | Less than 1 |
Particle size (D80) | 5-25μm | Bulk specific gravity (g/ml) | 0.3-0.5 |
pH | 6~9 | Iron impurity content | <10ppm |
The high specific surface area activated carbon adopted in the invention is the commercial capacitor grade activated carbon which is also called super capacitor activated carbon. The super-capacitor activated carbon is generally called as super-activated carbon or carbon electrode material, has the characteristics of super-large specific surface area, concentrated pores, low ash, good conductivity and the like, and is suitable for manufacturing high-performance batteries, double-electric-layer capacitor products and carriers for heavy metal recovery; the capacitor has the characteristics of high-current quick charge and discharge of the capacitor, energy storage of the battery and long repeated service life, and electrons between the moving conductors are utilized to release current (without depending on chemical reaction) during discharge, so that a power supply is provided for equipment.
According to the invention, the specific surface area of the high specific surface area activated carbon is 1000-2G, may be, for example, 1000m2/g、1200m2/g、1500m2/g、1800m2/g、2000m2/g、2200m2/g、2300m2/g、2500m2/g、2800m2/g、3000m2/g、3100m2/g、3200m2/g、3300m2/g、3400m2/g or 3500m2The present invention is not intended to be exhaustive of the specific points included in the ranges, limited to space and for the sake of brevity, as well as the specific points between the above-described values.
The specific surface area of the high specific surface area activated carbon in the invention is preferably 3000-3500m2(iv)/g, more preferably 3300-3500m2The specific energy of the secondary battery can be further improved by adopting the further optimized high specific surface area activated carbon, so that the secondary battery has higher specific energy, rapid charge and discharge are realized, and the cycle life is prolonged.
According to the present invention, the conductive agent is present in the iodide positive electrode component in an amount of 1-20 parts by weight, for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts by weight, and specific values therebetween are not exhaustive, and for the sake of brevity, specific values included in the ranges are not intended to be exhaustive.
In the present invention, any electron conductive material that does not adversely affect the battery performance can be used as the conductive agent. For example, carbon black such as acetylene black or ketjen black may be used, and conductive materials such as natural graphite (scale graphite, flake graphite, and earthy graphite), artificial graphite, carbon whiskers, carbon fibers, metal (copper, nickel, aluminum, silver, and gold) powders, metal fibers, and conductive ceramic materials may be used. In particular, any one of them may be used, or two or more of them may be contained as a mixture.
According to the present invention, the conductive agent is preferably a carbon material, which is commercially available, and the source of the conductive agent is not particularly limited.
The invention adopts cheap and easily available carbon material as conductive material, compared with conductive material such as three-dimensional graphite, the carbon material can greatly reduce the cost of the battery, and can be widely applied to industrial production.
According to the present invention, the carbon material may be selected from any one or a combination of at least two of graphite powder, carbon nanotube, graphene, conductive carbon black or nano carbon powder, and may also adopt any one or a combination of at least two of carbon quantum dot, activated carbon, carbon fiber, carbon aerogel, mesoporous carbon, carbon black, mesocarbon microbeads or hard carbon, for example, may be any one of graphite powder, carbon nanotube, graphene, conductive carbon black or nano carbon powder, and a typical but non-limiting combination is: graphite powder and carbon nano-tube, graphene and conductive carbon black, graphite powder and nano-carbon powder, carbon nano-tube and conductive carbon black, carbon nano-tube, graphene and nano-carbon powder and the like.
The conductive agent in the present invention is preferably any one or a combination of at least two of carbon nanotube, graphene, conductive carbon black or nano carbon powder, such as any one of carbon nanotube, graphene, conductive carbon black or nano carbon powder, and a typical but non-limiting combination is: carbon nano tubes and graphene, conductive carbon black and nano carbon powder, graphene and conductive carbon black, carbon nano tubes and nano carbon powder and the like.
According to the present invention, the binder is present in the iodide cathode component in an amount of 1-10 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts by weight, and specific values therebetween are not intended to be exhaustive for the sake of brevity and clarity.
According to the invention, the binder may be selected from carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) in a ratio of CMC to SBR of (0.5-5: 1, e.g. 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, and may be any of polyvinylidene fluoride (PVDF), L a133, L a 132.
L A132 and L A133 are both a capacitor binder produced by Tokydile, an aqueous dispersion of an acrylonitrile multipolymer.
The binder of the present invention is preferably polyvinylidene fluoride (PVDF) because of its good stability and corrosion resistance. The amount of the positive electrode active material added is usually 1 to 30% by mass based on the mass of the positive electrode active material.
According to the invention, the positive current collector can adopt any one of aluminum foil, carbon-coated aluminum foil, foamed aluminum, carbon paper, carbon-plastic composite film or carbon fiber felt.
The electrolyte adopts an ionic liquid electrolyte which is prepared by anhydrous aluminum halide and a general formula of [ X]+Z-The chemical reaction of the organic salt of (1) can be expressed by the following equation:
AlT3+[X]+Z-→[X]+[AlT3Z]-
wherein the anhydrous aluminum halide has a general formula of AlT3Wherein T represents any of F, Cl, Br or IMeaning one or a combination of at least two, which may be, for example, any of F, Cl, Br or I, with typical but non-limiting combinations being: f and Cl, Cl and Br, Br and I, F, Cl and Br.
Illustratively, the anhydrous aluminum halide is AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one or a combination of at least two of I, for example, AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one of, typically but not limited to, combinations of I: AlBr3And AlCl3,AlI3And AlF3,AlFBr2、AlF2Br and AlFCl2,AlICl2And AlIBr2,AlI2Br and AlFBr2,AlF2Cl、AlFI2And AlF2I。
According to the invention, the organic salt which is reacted with the anhydrous aluminium halide is of the general formula [ X]+Z-Wherein [ X ]]+Represents an organic cation, Z-Represents an anion; the organic cation is any one or combination of at least two of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium salt ion or quaternary phosphonium salt ion, and is preferably quaternary ammonium salt ion; the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them.
The organic salt is selected to be the same as that used in the preparation of the iodide in the iodide cathode composition as described above.
The ionic liquid electrolyte of the present invention can be prepared by the following method, but is not limited thereto:
(a) separate quantification of anhydrous aluminum halide and organic salt [ X ]]+Z-Controlling the anhydrous aluminum halide and the organic salt [ X ]]+Z-The molar ratio of (1-2) to (1), putting the two into a closed container, wherein the closed container needs to be filled with inert gas which is one or a mixture of two of nitrogen and argon;
(b) heating the sealed container, controlling the temperature at 50-200 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
According to the invention, the ionic liquid electrolyte is preferably prepared by the method, and the method has the advantages that: the method can be completed in a closed container, such as a high-pressure reaction kettle, at one time through one-time feeding, does not need purification, evaporation, filtration and other processes, and has the advantages of high production efficiency, high yield, short production period and low investment.
In the preparation process of the ionic liquid electrolyte, the anhydrous aluminum halide and the organic salt [ X ] in the step (a)]+Z-Is (1-2):1, and may be, for example, 1:1, 1:1.5 or 2:1, and the particular values between the above values, are not exhaustive and the invention is not intended to be limited to the specific values included in the ranges set forth for brevity and clarity.
In the preparation process of the ionic liquid electrolyte solution of the present invention, the closed container in step (a) may be a closed container known in the art, for example, a high pressure reactor, and is not particularly limited herein.
In the preparation of the ionic liquid electrolyte of the present invention, the temperature in step (b) is controlled to be 50-200 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 90 ℃, 100 ℃, 110 ℃, 122 ℃, 135 ℃, 150 ℃, 170 ℃, 185 ℃ or 200 ℃, and the specific values therebetween are limited to the space and for the sake of brevity, and the present invention is not exhaustive.
According to the invention, the negative electrode is a metal negative electrode or a metal alloy negative electrode.
The metal negative electrode in the present invention may be selected from any one of lithium, sodium, magnesium, or aluminum.
The metal alloy cathode in the invention is a metal alloy cathode containing any one or at least two of lithium, sodium, magnesium or aluminum, and preferably any one of a magnesium aluminum alloy cathode, a lithium aluminum alloy cathode or a zinc lithium alloy cathode.
As the separator, a porous film is used, and a microporous polymer film or nonwoven fabric is generally preferably used. Particularly preferred is a porous film made of a polyolefin polymer. Specifically, there may be mentioned microporous films made of polyethylene or polypropylene, multilayer films of porous polyethylene films and polypropylene films, nonwoven fabrics made of polyester fibers, aromatic polyamide fibers, glass fibers, etc., and nonwoven fabrics having ceramic fine particles of silica, alumina, titania, etc. attached to the surfaces thereof.
According to the present invention, it is preferable to use any one of a micro glass fiber separator, a polyolefin non-woven fabric separator, a polyvinylidene fluoride separator, a cellulose separator, or a commercial lithium ion battery separator.
The aluminum-plastic film used in the invention can be any one of an aluminum shell, an aluminum alloy aluminum-plastic film, a plastic aluminum-plastic film, a stainless steel shell, a stainless steel plastic composite aluminum-plastic film or a nickel-plated steel shell, and any aluminum-plastic film material known in the art is suitable for the invention, and is not limited in particular.
In a second aspect, the invention also provides an assembly method of the iodide pouch battery as described in the first aspect, the assembly method comprising the following steps:
(1) assembling the battery pole group by adopting a lamination or winding mode;
(2) the positive electrode lug or the negative electrode lug is bonded with the aluminum plastic film through a hot melting process;
(3) the aluminum-plastic film is molded by punching and hot pressing, and the battery pole group is sealed in the aluminum-plastic film;
(4) and injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging to obtain the battery.
The method for assembling the iodide pouch battery in the present invention is preferably as described above, and the assembly may be performed by a technique known in the art.
The battery pole group can be assembled in a lamination mode or a winding mode, the assembly method of the lamination mode is to alternately distribute the positive pole and the negative pole, and the positive pole and the negative pole are separated by a diaphragm; alternatively, the winding method is an assembly method in which the positive electrode and the negative electrode are separated by a separator and wound to form a square structure.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the iodide provided by the invention is used as a novel chemical system and exists in the positive active material of the battery in a liquid form. By adding the iodide into the positive active material, the theoretical specific energy of the positive active material can reach 211mAh/g, so that the prepared secondary battery has higher specific energy, realizes quick charge and discharge, has long cycle life and low raw material cost;
(2) the preparation method of iodide provided by the invention can be completed in a closed container at one time by one-time feeding, does not need purification, evaporation, filtration and other processes, and has the advantages of high production efficiency, high yield, short production period and low investment.
Drawings
Fig. 1 is a schematic external view of an iodide pouch battery according to the present invention;
FIG. 2 is a view showing a laminated type pole group structure of the battery of the present invention;
fig. 3 is a diagram showing a wound pole group structure of the battery of the present invention.
In the figure: 1-positive pole lug, 2-negative pole lug, 3-aluminum plastic film, 4-negative pole piece, 5-diaphragm and 6-positive pole piece.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The iodide used in the invention, the preparation method of the iodide and the iodide positive electrode component and the ionic liquid electrolyte and the assembly method of the iodide soft package battery are prepared on a laboratory scale by adopting the following general method:
general preparation of iodide:
(a) respectively taking an iodine simple substance and organic salt, controlling the molar ratio of the iodine simple substance to the organic salt to be (1-4):1, firstly putting the organic salt into a closed container, and introducing inert gas into the closed container, wherein the inert gas is preferably nitrogen and/or argon;
(b) adding iodine into a closed container, controlling the whole process to be 1-60min, stirring and cooling in the adding process, and controlling the temperature to be within 50 ℃;
(c) and after the iodine simple substance is added, cooling to room temperature to obtain the iodide.
The general composition of the iodide cathode component (comprising the following components in parts by weight):
the general preparation method of the ionic liquid electrolyte comprises the following steps:
(a) separate quantification of anhydrous aluminum halide and organic salt [ X ]]+Z-Controlling the anhydrous aluminum halide and the organic salt [ X ]]+Z-The molar ratio of (1-2) to (1), putting the two into a closed container, wherein the closed container needs to be filled with inert gas which is one or a mixture of two of nitrogen and argon;
(b) heating the sealed container, controlling the temperature at 50-200 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
Construction of iodide pouch cell:
an iodide pouch battery, comprising: the battery comprises a battery pole group, a positive pole tab, a negative pole tab, electrolyte and an aluminum-plastic film; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the positive electrode comprises a positive electrode current collector and an iodide positive electrode component coated on the surface of the positive electrode current collector.
The assembling method of the iodide soft package battery comprises the following steps:
(1) assembling the battery pole group by adopting a lamination or winding mode;
(2) the positive electrode lug or the negative electrode lug is bonded with the aluminum plastic film through a hot melting process;
(3) the aluminum-plastic film is molded by punching and hot pressing, and the battery pole group is sealed in the aluminum-plastic film;
(4) and injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging to obtain the battery.
Electrochemical results are as follows:
the target material was tested in a metal anode test electrochemical cell to determine the specific capacity of the positive active material and to determine if it has the ability to undergo charge-discharge cycling, and to perform a performance test on the iodide pouch cell.
As shown in fig. 1, the iodide pouch battery of the present invention comprises: the positive electrode tab 1, the negative electrode tab 2 and the aluminum-plastic film 3 are bonded together through a hot melting process, the aluminum-plastic film 3 is formed through punching and hot pressing, and the battery electrode group is sealed in the aluminum-plastic film.
Assembling the negative plate 4, the positive plate 6 and the diaphragm 5 in a laminating or winding mode to obtain a battery pole group, then injecting electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging by using an aluminum plastic film to obtain the iodide soft package battery.
Fig. 2 shows a battery pole group assembled by lamination, wherein 4 is a negative plate, 5 is a diaphragm, 6 is a positive plate, the positive plate 6 and the negative plate 4 are alternately distributed, and the middle is separated by the diaphragm 5.
Fig. 3 shows a battery pole group assembled by winding, wherein 4 is a negative plate, 5 is a diaphragm, 6 is a positive plate, the positive plate 6 and the negative plate 4 are separated by the diaphragm 5, and the pole group is wound into a square shape.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
A battery comprises a carbon electrode, a magnesium cathode, a polyvinylidene fluoride diaphragm, a cathode tab, an anode tab, an electrolyte and an aluminum-plastic film; the carbon electrode comprises an aluminum foil and an iodide cathode component coated on the surface of the aluminum foil.
The iodide positive electrode component comprises the following components in parts by weight: 80 parts of tetraethyl ammonium triiodide and high-specific-surface-area activated carbon (the specific surface area is 3500 m)2Per gram) 10 parts, 4 parts of conductive carbon black and 6 parts of PVDF; the electrolyte is prepared by mixing anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride salt according to the molar ratio of 2:1 for reaction.
The positive electrode containing the iodide positive electrode component adopts the following preparation method:
(1) placing tetraethyl ammonium triiodide, high specific surface area active carbon, conductive carbon black and PVDF into a ball milling tank, and carrying out ball milling for 72 min;
(2) adding N-methyl pyrrolidone into a ball milling tank, enabling the mass ratio of the total mass of tetraethyl ammonium triiodide, the high-specific-surface-area activated carbon, the conductive carbon black and the PVDF to the mass of the N-methyl pyrrolidone to be 50:50, and carrying out ball milling for 60min to obtain anode slurry;
(3) coating the positive electrode slurry on an aluminum foil, and controlling the coating thickness of one side to be 150 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and baking in vacuum at the vacuum degree of-0.09 MPa, the temperature of 120 ℃ and the time of 350 min;
(5) and extruding the dried pole piece by using a double-roll machine, and controlling the pressure of the double rolls to be 300 tons to obtain the carbon electrode containing the iodide anode component.
Alternately distributing carbon electrodes and magnesium cathodes, separating the carbon electrodes and the magnesium cathodes by polyvinylidene fluoride diaphragms, assembling a battery electrode group in a laminating mode, bonding a positive electrode tab or a negative electrode tab with an aluminum-plastic film through a hot melting process, forming the aluminum-plastic film through pit punching and hot pressing, and sealing the battery electrode group in the aluminum-plastic film; and then injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging by using an aluminum plastic film to obtain the iodide soft package battery.
The preparation method of tetraethyl ammonium triiodide comprises the following steps:
(a) respectively taking an iodine simple substance and tetraethylammonium iodide, controlling the molar ratio of the iodine simple substance to the tetraethylammonium iodide to be 1:1, firstly putting the tetraethylammonium iodide into a high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) adding iodine into a high-pressure reaction kettle, controlling the whole process to be 55min, stirring and cooling in the adding process, and controlling the temperature to be within 50 ℃;
(c) and after the iodine simple substance is added, cooling to room temperature to obtain the tetraethyl ammonium triiodide.
The preparation method of the ionic liquid electrolyte comprises the following steps:
(a) respectively quantifying anhydrous aluminum halide and 1-ethyl-3 methyl-imidazole chloride salt, controlling the molar ratio of the anhydrous aluminum halide to the organic salt to be 2:1, placing the anhydrous aluminum halide and the organic salt into a sealed high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) heating the high-pressure reaction kettle, controlling the temperature at 150 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
Example 2
In contrast to example 1, in the preparation method of iodide, the raw material organic salt is N-ethyl-N-butyl morpholine iodide, and iodide is N-ethyl-N-butyl morpholine triiodide, and the rest is the same as example 1.
Example 3
In contrast to example 1, in the preparation method of iodide, the raw material organic salt was 1-ethyl-3-methyl-imidazolium iodide, and the iodide was 1-ethyl-3-methyl-imidazolium triiodide, which were otherwise the same as in example 1.
Example 4
In contrast to example 1, in the method for preparing iodide, the raw material organic salt is N-ethylpyridine iodide, and the iodide is N-ethylpyridine triiodide, which are otherwise the same as in example 1.
Example 5
In contrast to example 1, in the method of preparing iodide, the starting organic salt was tributylethyl phosphine iodide, and the iodide was tributylethyl phosphine triiodide, the other procedure being the same as example 1.
Example 6
Compared with the example 1, the mass ratio of the mesophase microspheres and the carbon nanotubes used as the carbon material is 5:1, and the rest is the same as the example 1.
Example 7
The procedure of example 1 was repeated except that sodium carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) were used as binders in a mass ratio of 2:1 and water was used as a solvent, as compared with example 1.
Example 8
The procedure of example 1 was repeated except that L A133 was used as a binder and water was used as a solvent, as compared with example 1.
Example 9
Compared with the embodiment 1, the iodide cathode component comprises the following components in parts by weight: 30 parts of N-ethyl pyridine triiodide and high-specific surface area active carbon (the specific surface area is 3000 m)2Per g)48 parts, 18 parts of carbon nano tube and 4 parts of PVDF; the electrolyte was prepared by mixing anhydrous aluminum chloride and 1-ethyl-3-methyl-imidazolium chloride in a molar ratio of 2:1, and the other steps were the same as in example 1.
Example 10
A battery comprises a carbon electrode, an aluminum negative electrode, an ultrafine glass fiber diaphragm, a positive pole, a negative pole, an electrolyte and a shell; the carbon electrode includes an iodide cathode composition coated on the surface of carbon paper.
The iodide positive electrode component comprises the following components in parts by weight: 52 parts of 1-ethyl-3-methyl-imidazole triiodide salt and high-specific-surface-area activated carbon (the specific surface area is 3000 m)2Per g)30 parts, 4 parts of carbon nano tube and 4 parts of PVDF; the electrolyte is prepared by mixing anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride salt according to the molar ratio of 2:1 for reaction.
The positive electrode containing the iodide positive electrode component adopts the following preparation method:
(1) putting 1-ethyl-3-methyl-imidazole triiodide, high-specific-surface-area activated carbon, carbon nanotubes and PVDF into a ball milling tank, and carrying out ball milling for 20 min;
(2) adding N-methyl pyrrolidone into a ball milling tank, enabling the mass ratio of the total mass of the 1-ethyl-3-methyl-imidazole triiodide salt, the high-specific-surface-area activated carbon, the carbon nano tubes and the PVDF to the N-methyl pyrrolidone to be 40:60, and carrying out ball milling for 100min to obtain anode slurry;
(3) coating the positive electrode slurry on an aluminum foil, and controlling the coating thickness of one side to be 50 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and baking in vacuum, wherein the vacuum degree is controlled to be-0.10 MPa, the temperature is controlled to be 102 ℃, and the time is controlled to be 180 min;
(5) and extruding the dried pole piece by using a double-roll machine, and controlling the pressure of the double rolls to be 100 tons to obtain the carbon electrode containing the iodide anode component.
Alternately distributing carbon electrodes and aluminum cathodes, separating the carbon electrodes and the aluminum cathodes by superfine glass fiber diaphragms, assembling a battery electrode group in a lamination mode, bonding a positive electrode lug or a negative electrode lug with an aluminum-plastic film through a hot melting process, forming the aluminum-plastic film through a pit and hot pressing, and sealing the battery electrode group in the aluminum-plastic film; and then injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging by using an aluminum plastic film to obtain the iodide soft package battery.
The preparation method of the 1-ethyl-3-methyl-imidazole triiodide salt comprises the following steps:
(a) respectively taking an iodine simple substance and 1-ethyl-3-methyl-imidazole iodonium salt, controlling the molar ratio of the iodine simple substance to the 1-ethyl-3-methyl-imidazole iodonium salt to be 1:1, firstly putting the 1-ethyl-3-methyl-imidazole iodonium salt into a high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) adding iodine into a high-pressure reaction kettle, controlling the whole process to be 60min, stirring and cooling in the adding process, and controlling the temperature to be within 50 ℃;
(c) and after the iodine simple substance is added, cooling to room temperature to obtain the 1-ethyl-3-methyl-imidazole triiodide salt.
The preparation method of the ionic liquid electrolyte comprises the following steps:
(a) respectively quantifying anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride, controlling the molar ratio of anhydrous aluminum halide to 1-ethyl-3 methyl-imidazole chloride to be 2:1, placing the anhydrous aluminum chloride and the 1-ethyl-3 methyl-imidazole chloride into a sealed high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) heating the high-pressure reaction kettle, controlling the temperature at 150 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
And (3) testing the battery performance:
the secondary batteries obtained in examples 1 to 10 were subjected to charge and discharge performance tests, and the specific results are shown in table 1.
And (4) testing standard: the battery was subjected to charge and discharge experiments, charged to 2.6V at 0.5C, discharged at 0.5C, and cut off to 1V, and the charge and discharge data are shown in table 1.
TABLE 1
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (25)
1. An iodide pouch battery, comprising: the battery comprises a battery pole group, a positive pole tab, a negative pole tab, electrolyte and an aluminum-plastic film; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the anode comprises an anode current collector and an iodide anode component coated on the surface of the anode current collector;
the iodide cathode composition comprises: iodide, high specific surface area activated carbon, a conductive agent and a binder;
the iodide is obtained by reacting an iodine simple substance with an organic salt, wherein the molar ratio of the iodine simple substance to the organic salt is (2-4) to 1; the organic salt has a general formula of [ X]+Z-(ii) a Wherein, [ X ]]+Represents an organic cationZi, Z-Represents an anion;
the organic cation is any one or the combination of at least two of imidazolium ions, pyrrolium ions, piperidinium ions, morpholinium ions, quaternary ammonium salt ions or quaternary phosphonium salt ions;
the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of;
the positive electrode is prepared by adopting the following method, and the method comprises the following steps:
(1) putting iodide, high specific surface area activated carbon, a conductive agent and a binder into a ball milling tank, and carrying out ball milling for 5-120 min;
(2) adding an organic solvent into a ball milling tank, enabling the mass ratio of the total mass of the iodide, the high specific surface area activated carbon, the conductive agent and the binder to the organic solvent to be (40-60) - (60-40), and carrying out ball milling for 60-120min to obtain anode slurry;
(3) coating the positive electrode slurry on a current collector, and controlling the coating thickness of one side to be 100-300 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and performing vacuum baking, wherein the vacuum degree is controlled to be-0.08 to-0.10 MPa, the temperature is controlled to be 100-;
(5) and extruding the dried pole piece by using a double-roller machine, and controlling the pressure of the double rollers to be 50-300 tons to obtain the anode containing the iodide anode component.
3. the battery of claim 1, wherein the organic cation is a quaternary ammonium ion.
4. The battery of claim 1, wherein the high specific surface area activated carbon has a specific surface area of 1000-2/g。
5. The battery of claim 4, wherein the high specific surface area activated carbon has a specific surface area of 3000-3500m2/g。
6. The battery according to claim 1, wherein the conductive agent is any one of graphite powder, carbon nanotubes, graphene, conductive carbon black or nano carbon powder or a combination of at least two of the graphite powder, the carbon nanotubes, the graphene, the conductive carbon black or the nano carbon powder.
7. The battery according to claim 6, wherein the conductive agent is any one of or a combination of at least two of carbon nanotubes, graphene, conductive carbon black, or nano carbon powder.
8. The battery of claim 1, wherein the binder is CMC used in combination with SBR or is any one selected from PVDF, L a133 or L a 132.
9. The battery of claim 8, wherein the binder is PVDF.
10. The battery according to claim 1, wherein the positive electrode current collector is any one of or a combination of at least two of aluminum foil, foamed aluminum, carbon paper, carbon-plastic composite film, or carbon fiber felt.
11. The battery of claim 1, wherein the electrolyte is an ionic liquid electrolyte obtained by reacting an anhydrous aluminum halide with an organic salt.
12. The battery of claim 11 wherein the anhydrous aluminum halide has the formula AlT3Wherein T represents any one or a combination of at least two of F, Cl, Br or I.
13. The cell of claim 12, wherein the anhydrous aluminum halide is AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one of or a combination of at least two of I.
14. The battery of claim 11, wherein the organic salt has the formula [ X [ ]]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion; the organic cation is any one or the combination of at least two of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium salt ion or quaternary phosphonium salt ion; the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them.
15. The battery of claim 14, wherein the organic cation is a quaternary ammonium ion.
16. The battery of claim 1, wherein the negative electrode is a metal negative electrode or a metal alloy negative electrode.
17. The battery of claim 16, wherein the metal negative electrode is any one of lithium, sodium, magnesium, or aluminum.
18. The battery of claim 16, wherein the metal alloy negative electrode is a metal alloy negative electrode comprising any one or at least two of lithium, sodium, magnesium, or aluminum.
19. The battery of claim 18, wherein the metal alloy negative electrode is any one of a magnesium aluminum alloy negative electrode, a lithium aluminum alloy negative electrode, or a zinc lithium alloy negative electrode.
20. The battery according to claim 1, wherein the separator is any one of an ultra-fine glass fiber separator, a polyolefin non-woven fabric separator, a polyvinylidene fluoride separator, or a cellulose separator.
21. The battery of claim 1, wherein the separator is a commercial lithium ion battery separator.
22. The battery of claim 1, wherein the aluminum plastic film is any one of an aluminum case, an aluminum alloy aluminum plastic film, a plastic aluminum plastic film, a stainless steel case, a stainless steel plastic composite aluminum plastic film, or a nickel plated steel case.
23. A method of assembling a battery as claimed in any one of claims 1 to 22, comprising the steps of:
(1) assembling the battery pole group by adopting a lamination or winding mode;
(2) the positive electrode lug or the negative electrode lug is bonded with the aluminum plastic film through a hot melting process;
(3) the aluminum-plastic film is molded by punching and hot pressing, and the battery pole group is sealed in the aluminum-plastic film;
(4) and injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging to obtain the battery.
24. The method of claim 23, wherein the battery pole group is assembled in a stack by: the positive electrodes and the negative electrodes are alternately distributed, and the positive electrodes and the negative electrodes are separated by adopting a diaphragm.
25. The method of claim 23, wherein the battery pole group is assembled by winding: the positive electrode and the negative electrode were separated by a separator, and wound to form a square structure.
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Denomination of invention: Iodide soft pack battery and its assembly method Granted publication date: 20200717 Pledgee: Dongyang Branch of China Construction Bank Co.,Ltd. Pledgor: HENGDIAN GROUP DMEGC MAGNETICS Co.,Ltd. Registration number: Y2024330001130 |
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