CN109449370A - One kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric - Google Patents
One kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric Download PDFInfo
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- CN109449370A CN109449370A CN201811110629.6A CN201811110629A CN109449370A CN 109449370 A CN109449370 A CN 109449370A CN 201811110629 A CN201811110629 A CN 201811110629A CN 109449370 A CN109449370 A CN 109449370A
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- fiber
- mno
- secondary cell
- weave
- battery
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- 239000004744 fabric Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 102
- 229910007613 Zn—MnO2 Inorganic materials 0.000 claims abstract description 19
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 15
- 238000010276 construction Methods 0.000 claims abstract description 6
- 238000009941 weaving Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 20
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- 238000005538 encapsulation Methods 0.000 claims description 9
- 229920003169 water-soluble polymer Polymers 0.000 claims description 9
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229910006287 γ-MnO2 Inorganic materials 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 229910006648 β-MnO2 Inorganic materials 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 229920001688 coating polymer Polymers 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229920000609 methyl cellulose Polymers 0.000 claims 1
- 239000001923 methylcellulose Substances 0.000 claims 1
- 239000012994 photoredox catalyst Substances 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 5
- 239000011245 gel electrolyte Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 4
- 238000009954 braiding Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910003144 α-MnO2 Inorganic materials 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000013305 flexible fiber Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
- D03D1/0088—Fabrics having an electronic function
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
- D03D15/247—Mineral
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
- D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
-
- 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/747—Woven material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/02—Cotton
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/20—Cellulose-derived artificial fibres
- D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2211/00—Protein-based fibres, e.g. animal fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
Abstract
The invention discloses one kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric；Characterized by comprising the following steps: 1) in cathode or the surface wrap non-conductive fibre of anode, the non-conductive fibre is isolated by cathode and anode；2) cathode obtained in step 1) and anode are discharged side by side；Cathode and anode are coated togather using polyelectrolyte gel, form the fiber electrode pair of package high-molecular gel；3) by the fiber electrode for wrapping up high-molecular gel to being packaged, the battery unit of fibre structure is formed；4) appearance of the battery unit after encapsulating obtained in step 3) is wound into clothing fiber to get Zn-MnO can be woven2Secondary cell；5) battery is connected into the fibre structure battery series connection group with required voltage；6) series connection of fibre structure battery is organized into the battery module of fabric construction, and the conducting wire fiber by being equally woven into cloth using shuttle weaving manner, further realizes being connected in parallel for fibre structure battery series connection group.
Description
Technical field
It is specifically a kind of to weave Zn-MnO the present invention relates to wearable flexible field of power supplies2Secondary cell and its power supply
The preparation method of fabric.
Background technique
As the improvement of people's living standards, more and more flexible electronic components emerge in large numbers.At present wearable device by
People's pursues, and researchs and develops there are many company to it.This requirement to energy resource system is also higher and higher, than
Such as: the flexibility of energy source device, lasting power supply and the experience of good wearing.
Therefore, the exploitation for flexible energy storage device and the research of texturing energy module are also necessary.
Manganese dioxide is widely paid close attention in fields such as energy storage by people as a kind of important transition metal oxide,
It synthesizes the active manganese dioxide of high energy storage and extends the potential application of nano-manganese dioxide and have become the research hotspot of people.
With the development of portable wearable electronic device, the energy supply of such device is asked in realization there is also some at present
Topic.Such as energy supply device flexibility is poor, and volume is big, and the performance of device is unstable in the case where deformation.And existing flexibility
Device belongs to plank frame more, so that wearing experience sharp fall.
So developing a kind of new structural energy-storage battery is necessary.
Zn-MnO2Battery is compared with other batteries, and manufacturing cost is low, abundant raw material and cheap, and manufacturing equipment is simple,
Thus attract attention rapidly.But due to traditional Zn-MnO2The limitation of battery structure and technique leads to the flexibility of battery
It is difficult to realize with large-scale integrated characteristic.
Summary of the invention
Present invention aim to address problems of the prior art, and Zn-MnO can be woven by providing one kind2Secondary cell
And its preparation method of power supply fabric.
To realize the present invention purpose and the technical solution adopted is that such, one kind can weave Zn-MnO2Secondary cell,
It is characterized in that: including fiber cathode, fiber anode and electrolyte；
The fiber cathode is the carbon based fibers material that surface coats active Mn oxide；
The fiber anode is the zinc-plated conducting fiber of zinc silk or surface；
The electrolyte is resulting polyelectrolyte gel after electrolyte solution drying and dehydrating；The electrolyte solution
In contain Zn2+、Mn2+、Li+And water soluble polymer.
Further, the carbon based fibers material is the fiber that carbon material is wrapped up on carbon fiber or surface；The carbon based fibers material
The diameter of material is 0.005~1mm；
When carbon based fibers material is the fiber that carbon material is wrapped up on surface, the thickness of the carbon material be 100nm~
0.1mm。
Further, the active Mn oxide includes a-MnO2、β-MnO2、γ-MnO2Or the mixing crystal form of three.
Further, in the electrolyte solution: zinc ion concentration is 0.4~3mol/L, manganese ion concentration be 0.1~
1mol/L, lithium concentration are 0.2~3mol/L, water soluble polymer content is 5~1000g/L；
The water soluble polymer includes polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylamide (PAM), poly- third
Acrylamide (HPAM), para-aminophenol (PAP), polyethylene glycol oxide (PEO), anionic polyacrylamide (APAM), polyetherimide
Amine (PEI), polyethylene glycol (PEG), polymaleic anhydride, carboxymethyl starch, acetic starch, hydroxymethyl cellulose, carboxymethyl cellulose
One or more of element, polyamino resin or amino resins.
Further, during the electrolyte solution drying and dehydrating obtains polyelectrolyte gel: dry temperature
It is 70 DEG C~120 DEG C, the time is 30min~300min.
One kind can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the following steps are included:
1) in fiber cathode or the surface wrap non-conductive fibre of fiber anode, the non-conductive fibre by cathode and anode every
From；
2) fiber cathode obtained in step 1) and fiber anode are discharged side by side；Using polyelectrolyte gel by two
Person is coated togather, and forms the fiber electrode pair of package high-molecular gel；
3) fiber electrode that high-molecular gel is wrapped up obtained in step 2) is formed into the electricity of fibre structure to being packaged
Pool unit；
4) appearance of the battery unit after encapsulating obtained in step 3) is wound into clothing fiber, obtains target product.
Further, in the step 1) non-conductive fibre diameter be 0.01~0.5mm, be divided between winding 0.005mm~
0.5mm, material are cotton thread, biomass fiber or synthetic line.
Further, the encapsulation process in the step 3) is that fiber electrode is packaged in plastic bushing or is directly coated high
The battery unit of molecule encapsulating material formation fibre structure；
When being packaged using plastic bushing, the plastic bushing is heat-shrink tube or thermosetting plastics pipe, the plastics
The internal diameter of casing is 0.1~10mm；The encapsulation at casing both ends can be using heat-sealing and other packaged types.
Gel electrolyte is injected into casing first, then respectively inserts cathode and anode respectively from the both ends of plastic bushing
Enter in plastic bushing；Then heating so that heat-shrink tube reduce, finally using etc. heat molten types high molecular material or polymeric sol pair
Casing both ends are packaged.
When being packaged using polymer encapsulation material, the polymer encapsulation material includes polymethyl methacrylate
(PMMA), ethylene-vinyl acetate copolymer (EVA), dimethyl silicone polymer (PDMS), polycarbonate (PC), marine glue, PS
One or more of glue, PA glue, PP glue, PC glue, PE glue, polyurethane adhesive, epoxide-resin glue, phenoxy resin or EP rubbers.
Method for coating can be spraying, brush solution or melten gel containing high molecular material, be also possible to directly coat heat
The high molecular material of fusibleness.
Further, in the step 4) battery unit appearance wind clothing fiber include cotton thread, polyester thread, linen thread,
Knitting wool, silk thread, leather line, chemical fibre line, union twist yarn or Modal line；The diameter of the clothing fiber is 0.003~3mm.
A kind of Zn-MnO of fabric construction2The preparation method of secondary cell, which comprises the following steps:
1) Zn-MnO can be woven2Secondary cell is connected into fibre structure battery series connection group；The fibre structure battery strings
Connection group has required voltage；
2) shuttle weaving manner is utilized, the series connection of fibre structure battery obtained in step 1) is organized into the electricity of fabric construction
Pond group module；
3) the fibre structure battery series connection group can further realize parallel connection by being equally woven into the conducting wire fiber of cloth
Connection.
The solution have the advantages that unquestionable, the invention has the following advantages that
1) raw material of the invention are from a wealth of sources, at low cost, light weight, can with Free Transform, be easy to series-parallel honest and clean
The flexible fiber of valence, particularly suitable for the integrated battery module for being woven into fabric construction；
2) in the present invention battery packaging method, it is easy to operate, to the of less demanding of equipment, production cost relative moderate,
Battery after encapsulation has light, beautiful, small and exquisite feature, can be used for being woven into energy storage textile；Moreover, it will not also produce
Raw toxic gas, it is environmentally friendly.
Therefore preparation and packaging method of the invention, has the characteristics that flexible and light, answers in the battery with extremely strong
With value.
Detailed description of the invention
Fig. 1 is that one kind can weave Zn-MnO2The production flow diagram of secondary cell；
Specific embodiment
Below with reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1:
One kind can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the following steps are included:
1) by α-MnO2N-Methyl pyrrolidone (NMP) is added in powder, acetylene black, Kynoar, is uniformly mixed and surpasses
Sound dispersion；It is then coated on fiber electrode surface, electrode sufficiently dry after the completion of coating, it is complete to solvent volatilization；
2) cotton thread for the low-density that thickness is 0.1mm, winding pitch 0.01mm are then wound in zinc electrode；
3) cathode obtained in step 2) and anode are discharged side by side；Using polyelectrolyte gel by cathode and anode
It is coated togather, forms the fiber electrode pair of package high-molecular gel；
In electrolyte solution containing zinc ion concentration be 2mol/L, manganese ion concentration 0.4mol/L, lithium concentration are
2mol/L, added water soluble polymer are PVA, content 100g/L.
During the electrolyte solution drying and dehydrating obtains polyelectrolyte gel: dry at being 85 DEG C in temperature
2h；
4) fiber electrode that high-molecular gel is wrapped up obtained in step 3) is formed into the electricity of fibre structure to being packaged
Pool unit；
It is packaged using heat-shrink tube, gel electrolyte is injected into heat-shrink tube first, then by two electrodes from heat
The both ends of the draw are inserted into heat-shrink tube respectively, in order to separate two electrodes, wind cotton thread in zinc electrode wherein for separating electricity
Pole prevents short circuit；Then heating is so that heat-shrink tube diminution, is finally packaged heat-shrink tube both ends with colloidal sol rifle；
5) Zn-MnO can be woven2Secondary cell is connected into the fibre structure battery series connection group with 3.8V voltage, then
2 groups of fibre structure battery series connection are organized into cloth using shuttle braiding, the conducting wire fiber by being equally woven into cloth carries out simultaneously
Connection connection；
Gained fabric battery module, output voltage 3.8V can drive electronic calculator work 2h (can be with after fully charged
Discharge 40min under 0.0002A discharge current).
Embodiment 2:
One kind can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the following steps are included:
1) by α-MnO2N-Methyl pyrrolidone (NMP) is added in powder, acetylene black, Kynoar, is uniformly mixed and surpasses
Sound dispersion；It is then coated on fiber electrode surface, electrode sufficiently dry after the completion of coating, it is complete to solvent volatilization；
2) cotton thread for the low-density that thickness is 0.01mm, winding pitch 0.008mm are then wound in zinc electrode；
3) cathode obtained in step 2) and anode are discharged side by side；Using polyelectrolyte gel by cathode and anode
It is coated togather, forms the fiber electrode pair of package high-molecular gel；
In electrolyte solution containing zinc ion concentration be 1mol/L, manganese ion concentration 0.6mol/L, lithium concentration are
2mol/L, added water soluble polymer are PAA, content 300g/L.
During the electrolyte solution drying and dehydrating obtains polyelectrolyte gel: dry at being 80 DEG C in temperature
2h；
4) fiber electrode that high-molecular gel is wrapped up obtained in step 3) is formed into the electricity of fibre structure to being packaged
Pool unit；
It is packaged using coating；Coating packaged type are as follows: by two electrode runs parallel juxtapositions, with dropper plus gel electrolyte
Matter makes its covering uniformly in two parallel electrode surfaces, will be coated with two electrode packages of electrolyte with PMMA later.
5) Zn-MnO can be woven2Secondary cell is connected into the fibre structure battery series connection group with 5.4V voltage, then
Battery series connection is organized into cloth using shuttle braiding, the conducting wire fiber by being equally woven into cloth carries out parallel processing；Gained
Fabric battery module, output voltage 5.4V, work 10min can be charged the phone after fully charged (can discharge in 0.0003A
Discharge 20min under electric current).
Embodiment 3:
One kind can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the following steps are included:
1) by γ-MnO2N-Methyl pyrrolidone (NMP) is added in powder, acetylene black, Kynoar, is uniformly mixed and surpasses
Sound dispersion；It is then coated on fiber electrode surface, electrode sufficiently dry after the completion of coating, it is complete to solvent volatilization；
2) cotton thread for the low-density that thickness is 0.2mm, winding pitch 0.05mm are then wound in zinc electrode；
3) cathode obtained in step 2) and anode are discharged side by side；Using polyelectrolyte gel by cathode and anode
It is coated togather, forms the fiber electrode pair of package high-molecular gel；
In electrolyte solution containing zinc ion concentration be 2mol/L, manganese ion concentration 0.4mol/L, lithium concentration are
0.8mol/L, added water soluble polymer are PAM, content 100g/L.
During the electrolyte solution drying and dehydrating obtains polyelectrolyte gel: dry at being 85 DEG C in temperature
2h；
4) fiber electrode that high-molecular gel is wrapped up obtained in step 3) is formed into the electricity of fibre structure to being packaged
Pool unit；
It is packaged using coating；Coating packaged type are as follows: by two electrode runs parallel juxtapositions, with dropper plus gel electrolyte
Matter makes its covering uniformly in two parallel electrode surfaces, will be coated with two electrode packages of electrolyte with EVA later.
5) Zn-MnO can be woven2Secondary cell is connected into the fibre structure battery series connection group with 3V voltage, then sharp
The series connection of fibre structure battery is organized into cloth, gained fabric battery module, output voltage 3V, after fully charged with shuttle braiding
Electronic watch can be driven to work 1h (can discharge 60min under 0.0001A discharge current).
Embodiment 4:
One kind can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the following steps are included:
1) by α-MnO2N-Methyl pyrrolidone (NMP) is added in powder, acetylene black, Kynoar, is uniformly mixed and surpasses
Sound dispersion；It is then coated on fiber electrode surface, electrode sufficiently dry after the completion of coating, it is complete to solvent volatilization；
2) cotton thread for the low-density that thickness is 0.01mm, winding pitch 0.008mm are then wound in zinc electrode；
3) cathode obtained in step 2) and anode are discharged side by side；Using polyelectrolyte gel by cathode and anode
It is coated togather, forms the fiber electrode pair of package high-molecular gel；
In electrolyte solution containing zinc ion concentration be 3mol/L, manganese ion concentration 0.4mol/L, lithium concentration are
2mol/L, added water soluble polymer are PVA, content 100g/L.
During the electrolyte solution drying and dehydrating obtains polyelectrolyte gel: dry at being 85 DEG C in temperature
2h；
4) fiber electrode that high-molecular gel is wrapped up obtained in step 3) is formed into the electricity of fibre structure to being packaged
Pool unit；
It is packaged using coating；Coating packaged type are as follows: by two electrode runs parallel juxtapositions, with dropper plus gel electrolyte
Matter makes its covering uniformly in two parallel electrode surfaces, will be coated with two electrode packages of electrolyte with epoxide-resin glue later.
5) Zn-MnO can be woven2Secondary cell is connected into the fibre structure battery series connection group with 7.2V voltage, then
10 groups of fibre structure battery series connection are organized into cloth using shuttle braiding, the conducting wire fiber by being equally woven into cloth carries out simultaneously
Connection connection；Gained fabric battery module, output voltage 7.2V can drive remote control car work 10min (can after fully charged
With the 10min that discharges under 0.001A discharge current).
Claims (10)
1. one kind can weave Zn-MnO2Secondary cell, it is characterised in that: including the fiber cathode, fiber anode and electrolyte；
The fiber cathode is the carbon based fibers material that surface coats active Mn oxide.
The fiber anode is the zinc-plated conducting fiber of zinc silk or surface.
The electrolyte is resulting polyelectrolyte gel after electrolyte solution drying and dehydrating；Contain in the electrolyte solution
There is Zn2+、Mn2+、Li+And water soluble polymer.
2. one kind according to claim 2 can weave Zn-MnO2Secondary cell, it is characterised in that: the carbon based fibers material
The fiber of carbon material is wrapped up for carbon fiber or surface；The diameter of the carbon based fibers material is 0.005~1mm；
When carbon based fibers material is the fiber that carbon material is wrapped up on surface, the thickness of the carbon material is 100nm~0.1mm.
3. one kind according to claim 1 can weave Zn-MnO2Secondary cell, it is characterised in that: the activity Mn oxide
Including a-MnO2、β-MnO2、γ-MnO2Or the mixing crystal form of three.
4. one kind according to claim 1 can weave Zn-MnO2Secondary cell, it is characterised in that: the electrolyte solution
In: zinc ion concentration is 0.4~3mol/L, manganese ion concentration is 0.1~1mol/L, lithium concentration is 0.2~3mol/L, water
Soluble macromolecular content is 5~1000g/L；
The water soluble polymer includes polyvinyl alcohol, polypropylene, polyacrylamide, polyacrylamide, para-aminophenol, polyoxy
Change ethylene, anionic polyacrylamide, polyetherimide, polyethylene glycol, polymaleic anhydride, carboxymethyl starch, acetic starch, hydroxyl
One or more of methylcellulose, carboxymethyl cellulose, polyamino resin or amino resins.
5. one kind according to claim 1 can weave Zn-MnO2Secondary cell, it is characterised in that: the electrolyte solution is dry
It is dry dehydration obtain polyelectrolyte gel during: dry temperature be 70 DEG C~120 DEG C, the time be 30min~
300min。
6. one kind can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the following steps are included:
1) in fiber cathode or the surface wrap non-conductive fibre of fiber anode, the non-conductive fibre is isolated by cathode and anode；
2) fiber cathode obtained in step 1) and fiber anode are discharged side by side；The two is wrapped using polyelectrolyte gel
It overlays on together, forms the fiber electrode pair of package high-molecular gel；
3) fiber electrode that high-molecular gel is wrapped up obtained in step 2) is formed into the battery list of fibre structure to being packaged
Member；
4) appearance of the battery unit after encapsulating obtained in step 3) is wound into clothing fiber, obtains target product.
7. one kind according to claim 6 can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the step
It is rapid 1) in the diameter of non-conductive fibre be 0.01~0.5mm, be divided into 0.005mm~0.5mm between winding, material is cotton thread, biomass
Fiber or synthetic line.
8. one kind according to claim 6 can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the step
It is rapid 3) in encapsulation process be by fiber electrode be packaged in plastic bushing or directly coating polymer encapsulation material formed fiber
The battery unit of structure；
When being packaged using plastic bushing, the plastic bushing is heat-shrink tube or thermosetting plastics pipe, the plastic bushing
Internal diameter be 0.1~10mm；
When being packaged using polymer encapsulation material, the polymer encapsulation material includes polymethyl methacrylate, second
Alkene-acetate ethylene copolymer, polycarbonate, marine glue, PS glue, PA glue, PP glue, PC glue, PE glue, gathers dimethyl silicone polymer
One or more of urethane glue, epoxide-resin glue, phenoxy resin or EP rubbers.
9. one kind according to claim 6 can weave Zn-MnO2The preparation method of secondary cell, it is characterised in that: the step
It is rapid 4) in battery unit appearance winding clothing fiber include cotton thread, polyester thread, linen thread, woollen goods line, silk thread, leather line, chemical fibre
Line, union twist yarn or Modal line；The diameter of the clothing fiber is 0.003~3mm.
10. a kind of Zn-MnO of fabric construction2The preparation method of secondary cell, which comprises the following steps:
1) Zn-MnO can be woven2Secondary cell is connected into fibre structure battery series connection group；The fibre structure battery series connection group tool
There is required voltage；
2) shuttle weaving manner is utilized, the series connection of fibre structure battery obtained in step 1) is organized into the battery pack of fabric construction
Module；
3) the fibre structure battery series connection group can by being equally woven into the conducting wire fiber of cloth, further realize it is in parallel even
It connects.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811110629.6A CN109449370A (en) | 2018-09-21 | 2018-09-21 | One kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811110629.6A CN109449370A (en) | 2018-09-21 | 2018-09-21 | One kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113161624A (en) * | 2021-05-07 | 2021-07-23 | 哈尔滨工业大学 | Preparation method of elastic lithium battery with woven structure |
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|---|---|---|---|---|
| CN102881463A (en) * | 2012-08-14 | 2013-01-16 | 北京大学 | Fibrous supercapacitor and manufacturing method thereof |
| CN103700798A (en) * | 2013-12-16 | 2014-04-02 | 北京大学 | Fiber chemical energy storage power supply and preparation method thereof |
| CN104617336A (en) * | 2015-02-12 | 2015-05-13 | 中国工程物理研究院化工材料研究所 | Linear flexible lithium ion battery and preparation method thereof |
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2018
- 2018-09-21 CN CN201811110629.6A patent/CN109449370A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881463A (en) * | 2012-08-14 | 2013-01-16 | 北京大学 | Fibrous supercapacitor and manufacturing method thereof |
| CN103700798A (en) * | 2013-12-16 | 2014-04-02 | 北京大学 | Fiber chemical energy storage power supply and preparation method thereof |
| CN104617336A (en) * | 2015-02-12 | 2015-05-13 | 中国工程物理研究院化工材料研究所 | Linear flexible lithium ion battery and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113161624A (en) * | 2021-05-07 | 2021-07-23 | 哈尔滨工业大学 | Preparation method of elastic lithium battery with woven structure |
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