CN114899506A - Preparation method of scalable fibrous quasi-solid-state water-based lithium ion battery - Google Patents

Preparation method of scalable fibrous quasi-solid-state water-based lithium ion battery Download PDF

Info

Publication number
CN114899506A
CN114899506A CN202210575329.5A CN202210575329A CN114899506A CN 114899506 A CN114899506 A CN 114899506A CN 202210575329 A CN202210575329 A CN 202210575329A CN 114899506 A CN114899506 A CN 114899506A
Authority
CN
China
Prior art keywords
composite rope
lithium
fiber
elastic composite
hydrogel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210575329.5A
Other languages
Chinese (zh)
Other versions
CN114899506B (en
Inventor
黎俊
张昕晖
刘斯琦
黄玉东
胡桢
刘丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN202210575329.5A priority Critical patent/CN114899506B/en
Publication of CN114899506A publication Critical patent/CN114899506A/en
Application granted granted Critical
Publication of CN114899506B publication Critical patent/CN114899506B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • 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
    • H01M4/665—Composites
    • 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
    • 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
    • H01M4/75—Wires, rods or strips
    • 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
    • H01M2300/0002—Aqueous electrolytes
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A preparation method of a scalable fibrous quasi-solid-state water-based lithium ion battery belongs to the technical field of lithium ion batteries, and comprises the following steps: twisting the metal wire to obtain a metal twisted wire; respectively directly weaving the metal twisted yarns and the polymer fiber yarns to obtain composite ropes; the elastic body is taken as a shaft, and the metal twisted wires and the polymer fiber wires are woven to obtain the rope-shaped elastic composite rope with the coating structure; loading the positive electrode slurry on the surface of the elastic composite rope to obtain an elastic composite rope-positive electrode material combination; filling the mixture into a mould, injecting hydrogel prepolymerization liquid to initiate forming to obtain an elastic composite rope-anode material-hydrogel combination; drying the rope-shaped braided wire loaded negative electrode slurry to obtain a composite rope-negative electrode material combination; weaving the composite rope-cathode material assembly on the surface of the pre-extension elastic composite rope-anode material-hydrogel assembly, and filling and packaging the pre-extension elastic composite rope-anode material-hydrogel assembly into a sleeve. The battery has the advantages of millimeter magnitude, good flexibility, scalability and low manufacturing cost.

Description

Preparation method of scalable fibrous quasi-solid-state water-based lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a telescopic fibrous quasi-solid water-based lithium ion battery.
Background
Many small-size portable electronic equipment for example cell-phone, intelligent wrist-watch, intelligent glasses, bluetooth headset and portable sensor, heart pacemaker etc. are small-size dressed, implantation equipment owing to the particularity of its applicable environment, need further be the human adaptation, mostly nimble and soft structure, need satisfy soft, nimble requirement with the change of adaptation environment to its energy supply part equally. For wearable devices, there is a need for reliable safety, reducing adverse effects on the human body. Therefore, the energy supply equipment of the device has the characteristics of sufficient safety, such as no leakage, low toxicity, nonflammability and the like. At present, flexible energy storage devices mainly comprise a flexible super capacitor and a flexible battery, wherein the flexible super capacitor does not have an obvious working voltage platform and low energy density although having the characteristics of good cycle stability, quick charging, high power density and the like, and cannot be used for electronic devices needing a specific voltage interval; the flexible lithium ion battery has an obvious voltage working platform and can supply power for the energy storage device for a long time, but compared with the traditional hard shell battery and the polymer soft package battery, the flexible lithium ion battery still has the problem of low energy density. The flexible battery mainly has a plane (layered) structure and a fibrous structure, the number of the layered structures is large at present, and the preparation process is simple, namely, a current collector, a positive electrode, a negative electrode and an electrolyte/diaphragm are respectively prepared and stacked to form the flexible battery. The battery mainly has the bending and twisting functions, can realize larger capacity load, but for the battery, the thinner battery has better flexibility, but has capacity loss caused by dropping of electrode materials under repeated bending; for thicker layered flexible batteries, the flexibility on the thicker side is not good enough, which reduces some comfort for practical applications in flexible wearable devices. The fibrous battery can also realize flexible functions such as knotting and the like on the basis of bending and twisting, and is as soft as a rope, so that the comfort is greatly improved due to small volume. In addition, the one-dimensional fibrous lithium ion battery can be woven into a two-dimensional fabric structure, so that the use scene is further expanded. However, the preparation of the fibrous battery is difficult, the capacity is low, and the preparation of the fibrous lithium ion battery with high capacity at low cost by adopting a convenient method is still the target of research at present.
Due to its structural particularity, a one-dimensional fibrous lithium ion battery requires the design of each component thereof, including positive and negative current collectors, loaded electrode active materials, electrolyte/separator, and encapsulating materials. Most of the currently designed fibrous batteries use carbon nanotube material as a current collector, and support electrode active materials in a binder or binder-free manner. The preparation cost is increased due to the large use of carbon nanotube materials, and at present, no scalable fibrous lithium ion battery which adopts low-cost raw materials to realize a stable structure, can be prepared in a large scale and has high safety performance is available.
Disclosure of Invention
The invention aims to solve the problems of high preparation cost, poor safety and non-retractility of the conventional fibrous lithium ion battery, and provides a preparation method of a retractable fibrous quasi-solid water-based lithium ion battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a scalable fibrous quasi-solid-state water-based lithium ion battery comprises the following steps:
the method comprises the following steps: twisting a plurality of metal wires to obtain metal twisted wires;
step two: weaving metal twisted wires and polymer fiber wires to obtain a composite rope as a negative current collector; weaving metal twisted wires and polymer fiber wires on the surface of the elastomer to obtain an elastic composite rope as a positive current collector;
step three: drying the negative current collector loaded negative electrode slurry to obtain a composite rope-negative electrode material assembly;
step four: drying the positive pole slurry loaded by the positive pole current collector to obtain an elastic composite rope-positive pole material combination, filling the elastic composite rope-positive pole material combination into the surface of a mold, injecting hydrogel prepolymerization liquid to initiate polymerization to obtain the elastic composite rope-positive pole material-hydrogel combination;
step five: pre-stretching the elastic composite rope-positive electrode material-hydrogel assembly, and then weaving the composite rope-negative electrode material assembly to coat the composite rope-negative electrode material assembly to obtain a battery assembly;
step six: and (4) putting the battery assembly into a sleeve, and packaging the two ends of the sleeve.
In the first step, the metal wire is made of any one of 304 stainless steel, 304L stainless steel, 316L stainless steel, titanium or platinum, and the diameter of the metal wire is 0.02-0.1mm, preferably the diameter of the metal wire is 0.03-0.05mm, namely 304 stainless steel.
In the first step, the number of twisted strands is 4-12, preferably 4-8.
In the second step, the material of the polymer fiber line is one or more of polypropylene fiber, polyacrylonitrile fiber, polyvinyl formal fiber, polyamide fiber, polyethylene terephthalate, polyurethane fiber, aromatic polyamide fiber, aromatic polyester fiber, ultra-high molecular weight polyethylene fiber, poly (p-phenylene benzobisoxazole) (PBO fiber), polyimide fiber (PI fiber) or poly (p-phenylene pyridobisimidazole) (M5 fiber), and the titer of the polymer fiber line is 10D-1500D; preferably aramid fibers, aromatic polyester fibers, having a fineness of 100D to 400D.
In the second step, the total number of the spindles used for weaving is 6-24 spindles, preferably 8-16 spindles. The number of the weaving spindles of the elastic composite rope is 4-12, the number of the polymer fiber threads accounts for 1/6-1/2, preferably 4-8, of the number of the spindles, and the number of the spindles used by the polymer fiber threads accounts for 1/3-1/2. The number of weaving spindles of the composite rope is 4-8 spindles.
In the second step, the elastomer material is one or more of thermoplastic polyurethane elastomer (TPU), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-polyethylene-polypropylene-polystyrene block copolymer (SEPS), polyester thermoplastic elastomer (TPC), thermoplastic vulcanized rubber (TPV), natural rubber, styrene-butadiene rubber and polydimethylsiloxane, the elastomer is in a rope structure and is 1-6 of the above materials with the same diameter, and the diameter of each single elastomer is 0.3mm-1.0 mm.
In the third and fourth steps, the loading mode is one of brushing, spraying, dipping or electrophoretic deposition; the drying mode of the anode slurry is forced air drying or vacuum drying, the drying temperature is 80-120 ℃, and the drying time is 4-12 h; the drying mode of the cathode slurry is forced air drying or vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 4-12 h.
In the third step, the negative electrode slurry is composed of a negative electrode active material, a conductive material, a binder and a solvent. The negative active material in the negative slurry is vanadium dioxide (VO) 2 ) Vanadium pentoxide (V) 2 O 5 ) Lithium vanadate (LiV) 3 O 8 ) Polyimide (PI), titanium phosphate (Ti) 2 P 2 O 7 ) Lithium titanium phosphate (LiTi) 2 (PO 4 ) 3 ) Manganese dioxide (MnO) 2 ) Preferably, lithium titanium phosphate or lithium vanadate is used. The conductive material is one or more of conductive carbon black, acetylene black, vapor-grown carbon fiber, graphene, multi-walled carbon nanotube, carboxylated multi-walled carbon nanotube, hydroxylated multi-walled carbon nanotube and aminated multi-walled carbon nanotube, the solvent is one of N-methyl pyrrolidone, N-dimethyl formamide, N-dimethyl acetamide, acetone or water, when the solvent is one of N-methyl pyrrolidone, N-dimethyl formamide, N-dimethyl acetamide and acetone, the binder is one or more of polyvinylidene fluoride, polyvinylidene fluoride hexafluoropropylene copolymer and polyurethane, when the solvent is water, the binder is one or more of sodium carboxymethyl cellulose, sodium alginate, carboxymethyl chitosan, guar gum, carrageenan, styrene-butadiene rubber emulsion, polyacrylic acid, sodium hydrogen peroxide, sodium hydrogen carbonate, sodium hydrogen carbonate, sodium carbonate, One or more of sodium polyacrylate, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone. The mass ratio of the negative electrode active material to the conductive material to the binder is 70-90: 5-10: 5-20, the mass ratio of the total mass of the solid to the solvent is 50:80-400, the stirring mode is magnetic stirring or mechanical stirring, and the stirring time is 4-24 h.
In the fourth step, the positive electrode slurry is composed of a positive electrode active material, a conductive material, a binder and a solvent. The positive active material is spinel lithium manganate (LiMn) 2 O 4 ) Layered lithium manganate (LiMnO) 2 ) Lithium iron phosphate (LiFePO) 4 ) Lithium nickel cobalt manganese oxide (LiNi) x Co 1-2x Mn x O 2 ) Lithium nickel cobalt aluminate (LiNi) x Co 1-2x Al x O 2 ) Lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) Lithium nickelate (LiNiO) 2 ) Preferably, spinel lithium manganate and lithium iron phosphate are selected, the conductive material, the binder and the solvent are selected, and the step three is performed according to the mass ratio of the negative electrode active material, the conductive material and the binder, the mass ratio of the total solid mass to the solvent and the stirring mode.
In the fourth step, the hydrogel pre-polymerization solution is composed of a water-soluble polymer, an electrolyte, acrylamide, N-methylene bisacrylamide, an initiator and water. The dosage of the acrylamide accounts for 12-24% of the mass of the solvent. The amount of N, N-methylenebisacrylamide is 0.5 to 2%, preferably 1%, of the amount of acrylamide substance. The mass of the initiator solvent is 0.1-0.5%.
In the fourth step, the water-soluble polymer in the hydrogel prepolymerization solution is one or more of sodium alginate, sodium carboxymethylcellulose, polyvinyl alcohol, xanthan gum, agarose, polyethylene glycol, polyvinylpyrrolidone, gelatin, guar gum and carrageenan.
Fourthly, the electrolyte in the hydrogel pre-polymerization solution is lithium sulfate (Li) 2 SO 4 ) Or lithium nitrate (LiNO) 3 ). When the electrolyte in the hydrogel pre-polymerization solution is lithium sulfate, the concentration is 0.5-2 mol.L -1 When lithium nitrate is used, the concentration is 2-6 mol.L -1 Preferably 1 to 1.5 mol.L -1 And (3) lithium sulfate.
Fourthly, initiating polymerization by the hydrogel prepolymer liquid in one of heating, plasma, radiation, microwave and illumination modes; when the initiation mode is thermal initiation, the initiator uses one of ammonium persulfate, potassium persulfate, sodium persulfate and azodiisobutylamine hydrochloride, a catalyst is added simultaneously, the catalyst is one of sodium bisulfite, sodium sulfite and tetramethylethylenediamine, and the mass of the catalyst is 0.1-0.5% of that of the solvent. The temperature is 25-80 ℃, and the polymerization time is 10min-3 h; when the initiation mode is photo-initiation, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, phenyl-2, 4, 6-trimethyl benzoyl lithium phosphite or ammonium persulfate is used as the initiator, the wavelength of the initiator is 254nm-405nm, and the polymerization time is 10min-3 h; the initiation mode is plasma, microwave and radiation without using an initiator, and the polymerization time is 10min-3 h.
And step four, molding the die, namely sleeving a thin-wall tubular die outside the elastic composite rope-positive electrode material combination, wherein the tubular die is made of one of polypropylene or low-density polyethylene, and the inner diameter of the plastic pipe is 3-8 mm. One side of the plastic pipe is provided with a gap. And injecting the hydrogel pre-polymerization solution into a thin-wall plastic tube in an injection mode. And removing the die after initiating the molding.
And fifthly, the pre-extension proportion of the elastic composite rope-positive electrode material-hydrogel assembly is 50% -400%, and preferably 100% -200%.
And sixthly, the sleeve is made of one of silica gel, latex or polyurethane.
And sixthly, the packaging material is one or more of Polyamide (PA), Polyester (PES), Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE) and polyester amide (PEA), ethylene-vinyl acetate copolymer (EVA) hot melt adhesive or polydimethylsiloxane.
Compared with the prior art, the invention has the beneficial effects that:
1. the gel electrolyte can play the roles of a diaphragm and the electrolyte at the same time, is flexible and low in toxicity, and the electrolyte cannot leak.
2. The anode and cathode materials are formed by mixing powder materials and solvents, and the application range of the anode and cathode materials is wide.
3. The battery assembly environment requirement is low, and the battery can be assembled in an air atmosphere.
4. The battery cladding structure is relatively stable.
5. The used raw materials have low cost and can be used for large-scale continuous production.
6. The energy storage capacity of the lithium ion battery is realized, the wearable device can be used as an energy storage device, and meanwhile, the environment strain capacity is good.
7. The battery has the advantages of millimeter magnitude, good flexibility, scalability and low manufacturing cost.
Drawings
FIG. 1 is a scanning electron micrograph of an elastic composite cord;
FIG. 2 is a schematic view of a hydrogel-injected pre-polymerized liquid tube-type mold;
FIG. 3 is a diagram showing the relationship between the specific capacity of a battery and the number of charge and discharge times;
FIG. 4 is a schematic diagram of voltage change under bending conditions of a battery;
fig. 5 is a schematic diagram of a battery series lighting LED lamp.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the following specific examples. Unless otherwise defined, the terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1:
(1) 8 stainless steel wires of 304 mm in diameter were twisted to obtain a metal twisted wire.
(2) And weaving 6 ingots of metal twisted wires and 6 ingots of 136D aramid fiber polymer wires to obtain the composite rope serving as a negative current collector. 6 ingots of metal twisted wires and 6 ingots of 136D aramid polymer wires are woven into an elastic composite rope as a positive current collector by taking 1 natural rubber elastomer with the diameter of 1.0mm and the pre-stretching of 150% as a shaft, as shown in figure 1. The elongation of the elastic composite rope is 80%.
(3) And dip-coating the elastic composite rope in the positive electrode slurry, slowly taking out, and vacuum-drying at 80 ℃ for 12h to obtain the elastic composite rope-positive electrode material combination. The proportion of the positive electrode slurry is 0.35g of lithium manganate, 0.05g of acetylene black, 0.10g of polyvinylidene fluoride and 1.9g of N-methyl pyrrolidone, and the magnetic stirring time is 6 hours.
(4) And (3) filling the elastic composite rope-positive electrode material combination into a mould, and carrying out photo-initiation forming on the hydrogel pre-polymerization liquid to obtain the hydrogel electrolyte. The mould is a low density polyethylene tube with an internal diameter of 4 mm. The hydrogel pre-polymerization solution adopts sodium alginate as water-soluble polymer and lithium sulfate as electrolyte. Adding 0.05g of sodium alginate into 5g of water, adding 0.55g of lithium sulfate after the sodium alginate is dissolved, removing bubbles after the lithium sulfate is fully dissolved, adding 1.2g of acrylamide, 2.6mg of N, N-methylene bisacrylamide and 0.0190g of 1, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and stirring and dissolving to obtain the hydrogel pre-polymerization liquid. The hydrogel prepolymer solution was filled into a syringe and injected into a plastic tube mold through a plastic tube mold slit as shown in fig. 2. And irradiating by 365nm wavelength light for 1h to initiate polymerization to obtain an elastic composite rope-anode material-hydrogel combination, and removing the plastic pipe type die.
(5) And (3) immersing the composite rope into the cathode slurry, then slowly taking out, and carrying out vacuum drying at 80 ℃ for 12h to obtain the composite rope-cathode material assembly. The proportion of the cathode slurry is 0.4g of lithium manganate, 0.05g of acetylene black, 0.05g of polyvinylidene fluoride and 0.95g of N-methyl pyrrolidone, and the magnetic stirring time is 8 hours.
(6) Weaving the composite rope-cathode material assembly on the surface of an elastic composite rope-anode material-hydrogel assembly with the pre-elongation of 80% to form a battery assembly with a coating structure, wherein the number of weaving spindles is 6.
(7) And (3) putting the battery assembly into a silica gel sleeve, and encapsulating the two ends of the positive and negative electrodes and the pore area of the sleeve by using EVA hot melt adhesive to prepare the telescopic fibrous quasi-solid-state water-system lithium ion battery.
The maximum specific discharge capacity of the battery at 0.1C is calculated according to the active material and is 40.58mAh/g, and the specific discharge capacity after the battery is cycled for 40 times is 30.24mAh/g, as shown in figure 3.
Example 2:
(1) 6 pieces of 316 stainless steel wire having a diameter of 0.05mm were twisted to obtain a metal twisted wire.
(2) And weaving 12 ingots of metal twisted wires and 12 ingots of 200D polyester polymer wires to obtain a composite rope as a negative current collector. 12 ingots of metal twisted wires and 12 ingots of 200D polyester polymer wires are woven into an elastic composite rope as a positive current collector by taking 3 pre-stretched SBS elastomers with the diameter of 0.5mm and the pre-stretching percentage of 200% as shafts. The elongation range of the elastic composite rope is 100%.
(3) And brushing positive slurry on the elastic composite rope, and drying the elastic composite rope for 10 hours in vacuum at 100 ℃ to obtain an elastic composite rope-positive material combination. The positive electrode slurry comprises 0.4g of lithium iron phosphate, 0.05g of acetylene black, 0.05g of polyvinylidene fluoride hexafluoropropylene copolymer, 0.05g of polyurethane and 1.6g of N, N-dimethylformamide, and is mechanically stirred for 6 hours.
(4) And (3) filling the elastic composite rope-positive electrode material assembly into a mould, and carrying out thermal initiation molding on the hydrogel prepolymer to obtain the elastic composite rope-positive electrode material-hydrogel assembly. The die is a polypropylene tube with an inner diameter of 5 mm. The hydrogel pre-polymerization solution adopts sodium carboxymethylcellulose as a water-soluble polymer and lithium nitrate as an electrolyte. 30g of water is added into 0.45g of sodium carboxymethylcellulose, 8.27g of lithium nitrate is added after the sodium carboxymethylcellulose is dissolved, bubbles are removed after the lithium nitrate is fully dissolved, and then 3g of acrylamide, 13mg of N, N-methylene-bisacrylamide, 0.03g of ammonium persulfate and 0.03g of tetramethylethylenediamine are added and stirred to be dissolved to obtain hydrogel pre-polymerization liquid. Quickly filling the hydrogel prepolymerization solution into an injector, injecting the hydrogel prepolymerization solution into a mold through a tubular mold gap, carrying out thermal initiation polymerization for 10min at 25 ℃ to obtain an elastic composite rope-anode material-hydrogel combination, and removing the tubular mold.
(5) And brushing the negative electrode slurry on the composite rope, and performing forced air drying at 60 ℃ for 10 hours to obtain a composite rope-negative electrode material combination. The preparation method of the cathode slurry comprises the steps of mechanically stirring 0.8g of lithium vanadate, 0.1g of acetylene black, 0.05g of sodium carboxymethylcellulose and 3.28g of water for 8 hours, and then adding 0.125g of 40% mass fraction butadiene styrene rubber aqueous dispersion and mechanically stirring for 4 hours.
(6) And weaving the composite rope-cathode material assembly on the surface of the elastic composite rope-anode material-hydrogel assembly with the pre-elongation of 100% to form a battery assembly with a coating structure, wherein the number of weaving spindles is 4.
(7) And (3) packaging the battery assembly into a polyurethane sleeve, and packaging the two ends of the positive and negative electrodes and the pore area of the sleeve by using PES hot melt adhesive to obtain the telescopic fibrous quasi-solid-state water-system lithium ion battery.
The cell had good flexibility with a discharge plateau of about 1.0V, as shown in fig. 4. Connecting two batteries in series can light up a small LED bulb as shown in fig. 5.
Example 3:
(1) 4 pieces of 316L stainless steel wire having a diameter of 0.05mm were twisted to obtain a metal twisted wire.
(2) And weaving 6 spindles of metal twisted wires and 4 spindles of 1500D polypropylene fiber polymer wires to obtain the composite rope. 6 spindles of metal twisted wires and 4 spindles of 1500D polypropylene fiber polymer wires are woven into the elastic composite rope by taking 4 pre-stretched 400 percent TPU elastomers with the diameter of 0.3mm as shafts. The elongation of the elastic composite cord was 160%.
(3) Spraying the anode slurry on the elastic composite rope, and drying for 7h at 90 ℃ in vacuum to obtain the elastic composite rope-anode material combination. The positive electrode slurry comprises 0.755g of layered lithium manganate, 0.05g of acetylene black, 0.15g of polyvinylidene fluoride hexafluoropropylene copolymer and 1.5g of acetone, and is mechanically stirred for 5 hours.
(4) And (3) placing the elastic composite rope-positive electrode material assembly into a mould, and carrying out radiation initiation molding on the hydrogel prepolymer to obtain the elastic composite rope-positive electrode material-hydrogel assembly. The die is a polypropylene tube with an inner diameter of 4 mm. The hydrogel pre-polymerization solution adopts guar gum as a water-soluble polymer and lithium sulfate as an electrolyte. Adding 20g of water into 0.05g of guar gum, adding 4.4g of lithium sulfate after dissolution, removing bubbles after full dissolution, and then adding 3.2g of acrylamide and 10mgN, N-methylene bisacrylamide for dissolution to obtain hydrogel pre-polymerization liquid. Quickly filling the hydrogel prepolymerization liquid into an injector, injecting the hydrogel prepolymerization liquid into a mold through a tubular mold gap, irradiating and polymerizing for 3 hours by gamma rays to obtain an elastic composite rope-anode material-hydrogel combination, and removing the tubular mold.
(5) Spraying the negative electrode slurry on the composite rope, and carrying out forced air drying at 75 ℃ for 8h to obtain a composite rope-negative electrode material combination. The preparation method of the negative electrode slurry comprises the steps of mechanically stirring 0.9g of polyimide, 0.05g of acetylene black, 0.1g of sodium polyacrylate and 6g of water for 4 hours.
(6) Weaving the composite rope-cathode material assembly on the surface of the elastic composite rope-anode material-hydrogel assembly with the pre-elongation of 160% to obtain the battery assembly, wherein the number of weaving ingots is 8.
(7) And (3) putting the battery assembly into a latex sleeve, and encapsulating the two ends of the positive electrode and the negative electrode and the pore area of the sleeve by using a polyesteramide hot melt adhesive to prepare the telescopic fibrous quasi-solid-state water-system lithium ion battery.
The battery has good charge and discharge stability under knotting and stretching conditions.
Example 4:
(1) 12 titanium wires having a diameter of 0.05mm were twisted to obtain metal twisted wires.
(2) And weaving 18 ingots of metal twisted wires and 4 ingots of 10D polyacrylonitrile fiber polymer wires to obtain the composite rope serving as a negative current collector. 18 ingots of metal twisted wires and 4 ingots of 10D polyacrylonitrile fiber polymer wires are woven into an elastic composite rope as a positive current collector by taking 6 pre-stretched latex elastomers with 300% of diameter of 0.8mm as shafts. The elongation of the elastic composite rope was 140%.
(3) And (3) carrying out electrophoretic deposition on the positive electrode slurry of the elastic composite rope, and carrying out vacuum drying at 110 ℃ for 9h to obtain an elastic composite rope-positive electrode material combination. The positive electrode slurry comprises 0.85g of lithium nickelate, 0.1g of acetylene black, 0.15g of polyvinylidene fluoride and 3.0g N-N-dimethylacetamide, and is magnetically stirred for 24 hours.
(4) And (3) placing the elastic composite rope-positive electrode material assembly into a mould, and carrying out radiation initiation molding on the hydrogel prepolymer to obtain the elastic composite rope-positive electrode material-hydrogel assembly. The mould is a low density polyethylene tube with an inner diameter of 8 mm. The hydrogel pre-polymerization solution adopts xanthan gum as water-soluble polymer and lithium sulfate as electrolyte. Adding 0.1g of xanthan gum into 20g of water, adding 3.3g of lithium sulfate after dissolving, removing bubbles after fully dissolving, and adding 2.6g of acrylamide and 10mgN, N-methylene-bisacrylamide for dissolving to obtain the hydrogel pre-polymerization solution. Quickly filling the hydrogel prepolymerization solution into an injector, injecting the hydrogel prepolymerization solution into a mold through a tubular mold gap, polymerizing for 30min under microwave to obtain an elastic composite rope-anode material-hydrogel combination, and removing the tubular mold.
(5) And (3) carrying out electrophoretic deposition on the composite rope to obtain negative electrode slurry, and carrying out forced air drying at 85 ℃ for 7h to obtain a composite rope-negative electrode material assembly. The preparation method of the cathode slurry comprises the steps of 0.7g of lithium titanium phosphate, 0.1g of acetylene black, 0.1g of polyvinylidene fluoride and 2g of N-methyl pyrrolidone, and magnetic stirring is carried out for 20 hours.
(6) Weaving the composite rope-cathode material assembly on the surface of an elastic composite rope-anode material-hydrogel assembly with the pre-elongation of 140% to obtain a battery assembly, wherein the number of weaving spindles is 6.
(7) And (3) putting the battery assembly into a silica gel sleeve, and encapsulating the two ends of the positive and negative electrodes and the pore area of the sleeve by using low-density polyethylene hot melt adhesive to prepare the telescopic fibrous quasi-solid-state water-system lithium ion battery.

Claims (10)

1. A preparation method of a scalable fibrous quasi-solid state water-based lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: twisting a plurality of metal wires to obtain metal twisted wires;
step two: weaving metal twisted wires and polymer fiber wires to obtain a composite rope as a negative current collector; weaving metal twisted wires and polymer fiber wires on the surface of the elastomer to obtain an elastic composite rope as a positive current collector;
step three: drying the negative current collector loaded negative electrode slurry to obtain a composite rope-negative electrode material assembly;
step four: drying the positive pole slurry loaded by the positive pole current collector to obtain an elastic composite rope-positive pole material combination, filling the elastic composite rope-positive pole material combination into the surface of a mold, injecting hydrogel prepolymerization liquid to initiate polymerization to obtain the elastic composite rope-positive pole material-hydrogel combination;
step five: pre-stretching the elastic composite rope-positive electrode material-hydrogel assembly, and then weaving the composite rope-negative electrode material assembly to coat the composite rope-negative electrode material assembly to obtain a battery assembly;
step six: and (4) putting the battery assembly into a sleeve, and packaging the two ends of the sleeve.
2. The method of claim 1, wherein the method comprises the steps of: in the first step, the metal wire is made of any one of 304 stainless steel, 304L stainless steel, 316L stainless steel, titanium or platinum; the number of twisted strands is 4-12.
3. The method of claim 1, wherein the method comprises the steps of: in the second step, the total number of spindles used for weaving the composite rope is 4-8 spindles, and the total number of spindles used for weaving the elastic composite rope is 6-24 spindles.
4. The method of claim 1, wherein the method comprises the steps of: in the second step, the elastomer is made of one or more of thermoplastic polyurethane elastomer, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene-styrene block copolymer, polystyrene-polyethylene-polypropylene-polystyrene block copolymer, polyester thermoplastic elastomer, thermoplastic vulcanized rubber, natural rubber, styrene-butadiene rubber and polydimethylsiloxane, the shape of the elastomer is rope-shaped, the total number of the used elastomers is 1-6, and the diameter of the single elastomer is 0.3-1.0 mm; the polymer fiber line is made of one or more of polypropylene fiber, polyacrylonitrile fiber, polyvinyl formal fiber, polyamide fiber, polyethylene terephthalate, polyurethane fiber, aromatic polyamide fiber, aromatic polyester fiber, ultra-high molecular weight polyethylene fiber, poly (p-phenylene benzobisoxazole) fiber, polyimide fiber or poly (phenylene pyridbisimidazole) fiber.
5. The method of claim 1, wherein the method comprises the steps of: in the third and fourth steps, the loading mode is one of brushing, spraying, dipping or electrophoretic deposition.
6. The method of claim 1, wherein the method comprises the steps of: in the third step, the negative active material in the negative slurry is one of vanadium dioxide, vanadium pentoxide, lithium vanadate, polyimide, titanium phosphate, lithium titanium phosphate and manganese dioxide; in the fourth step, the positive active material in the positive slurry is one of spinel lithium manganate, layered lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium vanadium phosphate and lithium nickel oxide.
7. The method of claim 1, wherein the method comprises the steps of: in the fourth step, the hydrogel pre-polymerization solution is composed of a water-soluble polymer, an electrolyte, acrylamide, N-methylene bisacrylamide, an initiator and water.
8. The method of claim 7, wherein the method comprises the steps of: the water-soluble polymer is one or more of sodium alginate, sodium carboxymethylcellulose, polyvinyl alcohol, xanthan gum, agarose, gelatin, guar gum and carrageenan; the electrolyte is lithium sulfate or lithium nitrate; when lithium sulfate is used, the concentration is 0.5 to 2 mol.L -1 When lithium nitrate is used, the concentration is 2-6 mol.L -1 (ii) a The initiating mode is one of heating, plasma, microwave, radiation or illumination; when the initiation mode is thermal initiation, the initiator uses one of ammonium persulfate, potassium persulfate, sodium persulfate and azodiisobutymidine hydrochloride, a catalyst is added simultaneously, the catalyst is one of sodium bisulfite, sodium sulfite and tetramethylethylenediamine, when the initiation mode is photo initiation, the initiator uses 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, phenyl-2, 4, 6-trimethyl benzoyl lithium phosphite or ammonium persulfate, and when the initiation mode is plasma, microwave and radiation, the initiator is not needed.
9. The method of claim 1, wherein the method comprises the steps of: and step four, sleeving a thin-wall tubular mold outside the elastic composite rope-positive electrode material combination, wherein the tubular mold is made of polypropylene or low-density polyethylene, the inner diameter of the plastic pipe is 3-5mm, a gap is formed in one side of the plastic pipe, injecting the hydrogel pre-polymerization solution into the thin-wall plastic pipe in an injection mode, and removing the mold after initiating molding.
10. The method of claim 1, wherein the method comprises the steps of: in the sixth step, the sleeve is made of one of silica gel, latex or polyurethane; the packaging material is one or more of polyamide, polyester, low-density polyethylene, high-density polyethylene, polyester amide, ethylene-vinyl acetate copolymer hot melt adhesive or polydimethylsiloxane.
CN202210575329.5A 2022-05-24 2022-05-24 Preparation method of telescopic fibrous quasi-solid water system lithium ion battery Active CN114899506B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210575329.5A CN114899506B (en) 2022-05-24 2022-05-24 Preparation method of telescopic fibrous quasi-solid water system lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210575329.5A CN114899506B (en) 2022-05-24 2022-05-24 Preparation method of telescopic fibrous quasi-solid water system lithium ion battery

Publications (2)

Publication Number Publication Date
CN114899506A true CN114899506A (en) 2022-08-12
CN114899506B CN114899506B (en) 2024-02-23

Family

ID=82725455

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210575329.5A Active CN114899506B (en) 2022-05-24 2022-05-24 Preparation method of telescopic fibrous quasi-solid water system lithium ion battery

Country Status (1)

Country Link
CN (1) CN114899506B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013046555A1 (en) * 2011-09-29 2013-04-04 パナソニック株式会社 Battery
US20140178726A1 (en) * 2011-10-13 2014-06-26 Lg Chem, Ltd. Cable-type secondary battery
CN103904357A (en) * 2014-03-09 2014-07-02 复旦大学 Stretchable linear lithium ion battery and preparation method thereof
CN110444822A (en) * 2019-08-15 2019-11-12 哈尔滨工业大学 A kind of preparation method of the quasi- solid-state Zinc ion battery of integration
CN113161624A (en) * 2021-05-07 2021-07-23 哈尔滨工业大学 Preparation method of elastic lithium battery with woven structure
WO2021163892A1 (en) * 2020-02-18 2021-08-26 深圳先进技术研究院 Flexible battery negative electrode and preparation method therefor, and flexible battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013046555A1 (en) * 2011-09-29 2013-04-04 パナソニック株式会社 Battery
US20140178726A1 (en) * 2011-10-13 2014-06-26 Lg Chem, Ltd. Cable-type secondary battery
CN103904357A (en) * 2014-03-09 2014-07-02 复旦大学 Stretchable linear lithium ion battery and preparation method thereof
CN110444822A (en) * 2019-08-15 2019-11-12 哈尔滨工业大学 A kind of preparation method of the quasi- solid-state Zinc ion battery of integration
WO2021163892A1 (en) * 2020-02-18 2021-08-26 深圳先进技术研究院 Flexible battery negative electrode and preparation method therefor, and flexible battery
CN113161624A (en) * 2021-05-07 2021-07-23 哈尔滨工业大学 Preparation method of elastic lithium battery with woven structure

Also Published As

Publication number Publication date
CN114899506B (en) 2024-02-23

Similar Documents

Publication Publication Date Title
CN110660965B (en) Negative plate and preparation method thereof, lithium ion battery and preparation method and application thereof
CN107093773B (en) Battery with a battery cell
KR102192082B1 (en) Anode active material, anode including the anode active material, and lithium secondary battery including the anode
CN110048174B (en) Gel battery electrolyte membrane and preparation method and application thereof
CN109713215B (en) Lithium-supplement negative plate, preparation method thereof and lithium ion battery
CN104617336A (en) Linear flexible lithium ion battery and preparation method thereof
Lu et al. The advance of fiber-shaped lithium ion batteries
CN103178284A (en) Liquid flow lithium sulfur secondary battery
CN105720296B (en) Electrode winding element, preparation method and nonaqueous electrolyte rechargeable battery
CN108321377A (en) Negative electrode slurry, preparation method and the secondary cell comprising it
CN111312971B (en) Diaphragm, secondary battery and preparation method thereof
CN109301320B (en) Composite solid electrolyte with vertical orientation of inorganic solid electrolyte and preparation method thereof
CN106711401A (en) Lithium-ion flexible-cell substrate-free positive plate and preparation method
CN116364852B (en) Battery pole piece, preparation method thereof, electrode assembly, battery and electricity utilization device
CN109192927A (en) A kind of sulfurized polyacrylonitrile film and binder free lithium-sulphur cell positive electrode prepared therefrom with hollow tubular nanofiber
KR20160051199A (en) Electrode-adhesive layer composite, method of producing the same, and secondary battery comprising the same
KR20150122293A (en) Anode binder for secondary battery, electrode for secondary battery and secondary battery comprising the same
CN103354296A (en) Ultralight polymer lithium ion battery and manufacturing method thereof
CN114899506B (en) Preparation method of telescopic fibrous quasi-solid water system lithium ion battery
CN112687958A (en) Long-endurance button lithium battery and manufacturing method thereof
CN117039206A (en) Sodium anode and cathode material water-based battery and preparation method thereof
CN113964290A (en) Lithium metal negative electrode, preparation method thereof and lithium metal battery
KR101665656B1 (en) Cathode Material for secondary battery, and Lithium secondary battery manufactured therefrom
CN113161624B (en) Preparation method of elastic lithium battery with woven structure
CN115241541B (en) Preparation method of in-situ thermal polymerization solid-state lithium sulfur battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant