CN111697274B - Integrated industrial-grade preparation method of fibrous water-based secondary battery - Google Patents

Integrated industrial-grade preparation method of fibrous water-based secondary battery Download PDF

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CN111697274B
CN111697274B CN202010419833.7A CN202010419833A CN111697274B CN 111697274 B CN111697274 B CN 111697274B CN 202010419833 A CN202010419833 A CN 202010419833A CN 111697274 B CN111697274 B CN 111697274B
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secondary battery
water system
electrode slurry
fiber
gel electrolyte
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CN111697274A (en
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彭慧胜
洪扬
王兵杰
陈培宁
程勋亮
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Fudan University
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
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    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/626—Metals
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    • 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
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  • Mechanical Engineering (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of water system secondary batteries, and particularly relates to an integrated industrial-grade continuous preparation method of a fiber water system secondary battery. According to the invention, various functional materials such as positive electrode slurry, negative electrode slurry, gel electrolyte and the like are simultaneously extruded and molded by a multi-channel liquid injection method, so that the integrated continuous construction of the fiber water system secondary battery is realized; meanwhile, a drafting post-treatment technology is adopted, so that multi-stage drafting treatment on the fiber water system secondary battery is realized for the first time, and the stability and the mechanical property of a device are improved; the integration of fiber drying and device packaging is realized by an online heat packaging technology. The invention realizes the rapid and stable integrated continuous construction of the fiber water system secondary battery, and the obtained fiber devices have excellent structural stability, so that the fiber devices can be mixed-woven with other chemical fibers or independently woven into fabrics, and have wide application prospect in the field of wearable electronics.

Description

Integrated industrial-grade preparation method of fibrous water-based secondary battery
Technical Field
The invention belongs to the technical field of water system secondary batteries, and particularly relates to an integrated industrial preparation method of a fibrous water system secondary battery.
Background
Wearable electronic devices have become the mainstream development direction of modern electronic industry, more and more modern electronic devices are developing towards the application requirements of miniaturization, light weight, flexibility and integration, and the development of light-weight and flexible wearable energy storage system becomes the bottleneck problem limiting the development of the field [1]. This is because conventional energy storage systems (supercapacitors and lithium ion secondary batteries) are rigid, bulk structures, inflexible, and bulky. The planar [2,3] and the fibrous [4,5] energy storage devices developed in recent years can meet the requirements of flexibility and light weight; especially, the fibrous energy storage device has some unique structural advantages, such as large deformation of bending, stretching and even three-dimensional distortion, and the like, is easy to integrate, and can form energy storage fabric with good flexibility and high air permeability through mature textile technology.
Although research on fibrous energy storage devices is concerned by academia and industry at present, the preparation methods reported at present are complex. Taking a fibrous lithium ion secondary battery as an example, the fibrous lithium ion secondary battery can only be manually prepared in a laboratory at present, the preparation process is often complex and the preparation efficiency is low, and large-scale continuous preparation cannot be realized; the existing preparation method comprises the multi-step procedures of loading of active substances, preparation of fiber electrodes, coating of gel electrolyte, assembly and packaging of an integral device and the like [6,7]. The complicated processes result in low preparation efficiency, high cost and incapability of industrial-grade mass production of the fibrous lithium ion secondary battery, and the length of the fibrous lithium ion secondary battery is limited to the centimeter level and the performance of the fibrous lithium ion secondary battery is not stable enough, so that the further development and the application of the fibrous lithium ion secondary battery are severely restricted. For example, almost all energy storage fabrics are currently constructed by implanting fabricated fibrous devices onto conventional fabrics because these fibrous devices have not been able to meet the requirements of the mechanized weaving process. In addition, the current fibrous lithium ion secondary battery mainly has two configurations of a wound type and a coaxial type [8]. The fibrous lithium ion secondary battery with the winding structure has the problem of insufficient mechanical structure stability, for example, two fibrous electrodes are easy to separate from each other in the bending deformation process to cause the disassembly of the whole device, and the contact between the two electrodes and even the disconnection can occur. The fibrous lithium ion secondary battery having a coaxial structure has a problem that matching of capacities of the inner and outer active materials is difficult, although the structural stability is good.
Above, the reported device structures (wound type and coaxial type) of the fibrous lithium ion secondary battery have their own disadvantages, and these limiting factors severely restrict the further development and scale application of the fibrous water-based secondary battery. And the current fibrous lithium ion secondary battery based on the organic electrolyte has potential risks of combustion and explosion. Therefore, the development of an industrial preparation process route suitable for the fibrous water system secondary battery solves the key technical problems of reliability and stability of structure and performance in the process from a laboratory to industrial scale-up production, and the like, and is a problem that the fibrous water system secondary battery must be solved when moving to the market.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a method for realizing a fiber water-based secondary battery by solution spinning integration. According to the invention, various functional materials including anode slurry, cathode slurry, gel electrolyte and the like are simultaneously extruded and molded by a multi-channel liquid injection method, so that the integrated continuous construction of the fiber water system secondary battery is realized; by adopting a drawing post-treatment technology, the multistage drawing treatment on the fiber water system secondary battery is realized for the first time, and the stability, the conductivity and the mechanical property of the device are improved; the integration of fiber drying and device packaging is realized through an online heat packaging technology. The invention can realize the industrial scale continuous preparation of the fiber water system secondary battery with stable structure and excellent performance. The technical scheme of the invention is specifically introduced as follows.
An integrated industrial preparation method of a fiber water system secondary battery comprises the following specific steps:
(1) Preparing electrode slurry: mechanically stirring a polymer binder, a carbon nano conductive material, a metal particle conductive agent and an electrode active material according to a certain proportion to obtain spinnable electrode slurry, wherein the positive electrode slurry and the negative electrode slurry are different in electrode active material and consistent in formula of other components;
(2) Preparing a water-based gel electrolyte spinning solution: dissolving lithium salt in a polymer high molecular water solution to obtain a water system gel electrolyte spinning solution with certain viscosity;
(3) Integrated continuous construction: the method comprises the following steps of (1) simultaneously extruding positive electrode slurry, negative electrode slurry and a water-based gel electrolyte spinning solution into a coagulating bath by using a porous composite spinneret plate, simultaneously forming a gel electrolyte and two fiber electrodes by using the coagulating bath, and simultaneously playing a role of a diaphragm by using the gel electrolyte so as to realize the integrated continuous preparation of the fiber water-based secondary battery; wherein each component unit in the porous composite spinneret plate consists of two identical parallel inner channels and an outer channel containing the parallel inner channels; the two parallel inner channels are used for realizing the extrusion molding of the electrode slurry, and the outer channel comprising the two parallel channels is used for realizing the extrusion molding of the water-based gel electrolyte;
(4) Post-drafting treatment: drafting the molded fiber water system secondary battery sample by a continuous multi-stage drafting technology;
(5) Drying and packaging: firstly, washing the drafted fiber water system secondary battery sample for multiple times, then partially drying the fiber water system secondary battery sample, and then packaging the partially dried fiber water system secondary battery sample on line by using continuous coating to obtain the fiber water system secondary battery.
In the invention, in the step (1), the polymer binder is selected from one or more of carboxymethyl cellulose, sodium alginate, polyacrylate, polyethylene glycol, styrene butadiene rubber or polytetrafluoroethylene; the carbon nano conductive material is a carbon nano tube and graphene; the metal particle conductive agent is selected from one of nano silver or nano copper; the anode material is selected from metal oxide MnO 2 、LiMnO 2 、Na 0.44 MnO 2 Or polyanionic compounds LiFePO 4 One of (1); the negative electrode material is selected from metal oxide TiO 2 、 Li 4 Ti 5 O 12 Or polyanionic compound LiTi 2 (PO 4 ) 3 、NaTi 2 (PO 4 ) 3 Or metal particle nano zinc.
In the invention, in the step (1), the content of the polymer binder is 3-12 wt percent by taking the total solid content in the electrode slurry as 100 percent; the content of the carbon nano tube is 30-65wt%, and the content of the graphene is 0-5wt%; the content of the metal particle conductive agent is 0-7wt%; the content of the positive electrode material or the negative electrode material is independently 20 to 50wt%.
In the invention, in the step (1), the solvent in the electrode slurry is water, the solid content of the electrode slurry is 20-40wt%, and the viscosity of the electrode slurry is 12000-20000 mPa.s.
In the invention, in the step (2), the polymer is selected from one or more of chitosan, polyvinyl alcohol, sodium alginate, sodium carboxymethylcellulose or polyethylene glycol; the lithium salt is selected from one or more of lithium perchlorate, lithium chloride, lithium sulfate or lithium nitrate.
In the invention, in the step (2), the viscosity of the aqueous gel electrolyte spinning solution is 6000 to 11000 mPa.s.
In the invention, in the step (3), the inner diameter of the external channel of each component unit in the porous composite spinneret plate is 1-2.5 mm; the distance between the outer walls of the two parallel inner channels is equal to the distance between the outer walls of the inner channels and the inner walls of the outer channels along the diameter direction, and the diameter ratio of the inner channels to the outer channels is 1/5-2/5.
In the present invention, in the step (3), the relative extrusion rate of the aqueous gel electrolyte spinning solution and the electrode slurry is 1/0.05 to 1/0.5.
In the present invention, in the step (4), the drawing ratio of the fibrous water-based secondary battery formed by the coagulation bath is 1 to 10 times, and the mechanical strength is 120 MPa.
In the invention, in the step (5), the water in the hydrogel fiber of the fiber water-based secondary battery is partially dried by air-blast drying, the water content is controlled to be 30 wt% -60 wt%, and the diameter of the fiber water-based secondary battery is controlled to be 200-600 mu m; and performing in-situ continuous online packaging on the fiber water system secondary battery by using one or more of polyurethane packaging glue, PEFE emulsion and PVDF emulsion, wherein the diameter of the packaged fiber water system secondary battery is 400-800 μm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention designs a porous composite spinneret plate, and realizes the extrusion molding of electrode slurry through two parallel channels with the same diameter in each component unit in the porous composite spinneret plate; extrusion molding of the polymer water-based gel electrolyte is achieved through an outer channel comprising the entire parallel channel;
(2) According to the invention, the electrode slurry with high conductivity, high energy storage capacity, rapid shear thinning, high yield stress and stable modulus is prepared by mixing the polymer binder, the carbon nano conductive material, the metal particle conductive agent, the anode material, the cathode material and other nano materials, and the rheological property of the slurry enables the carbon nano tubes in the slurry to be very easily oriented at a high shear rate and keep the orientation stable after forming, so that the conductivity and the mechanical strength of the fiber electrode are favorably improved;
(3) The aqueous gel electrolyte spinning solution is prepared by dissolving electrolyte salt in water-soluble polymer, and the gel electrolyte spinning solution not only needs to be solidified and formed to play roles of lithium ion conduction and mechanical support of gel electrolyte, but also can be used as a solidification bath of electrode slurry to simultaneously solidify and form the electrode slurry, so that the fibrous lithium ion battery is integrally constructed, and a good electrode-electrolyte interface is formed;
(4) The invention realizes the integrated industrial-grade preparation of the fiber water-based secondary battery by the technical process of simultaneously extruding and molding the water-based gel electrolyte spinning solution and two fiber electrodes, wherein the gel electrolyte simultaneously plays the role of a diaphragm;
(5) According to the invention, through a multi-stage drafting technology, the orientation of carbon nano conductive materials in electrode fibers and polymer chains in polymer gel electrolyte in a fiber water system secondary battery is improved, so that the conductivity of the electrode fibers and the mechanical property and stability of devices are improved;
(6) The preparation method has high production efficiency (more than 250 m/h/single spinneret orifice); the production stability is good, and the size and specific capacity of the obtained fibrous water system secondary battery are not greatly changed at the same production rate. The excellent stability and the continuous production technology enable the fabric to be easily mixed-woven with other fibers or independently woven into the energy storage fabric, so the fabric has wide application prospect in the field of wearable electronics.
Drawings
Fig. 1 is a schematic view of a process for integrally producing a fibrous aqueous secondary battery according to the present invention.
Fig. 2 is a structural diagram of each assembly unit in the spinneret plate in the embodiment.
Fig. 3 is a micrograph and a scanning electron micrograph of a cross section of the fibrous water-based secondary battery in the example.
FIG. 4 is a graph showing the relationship between the capacity ratio at different production speeds for each unit of the spinneret in the example.
FIG. 5 is a graph showing the relationship between the number of cycles and the specific capacity in the examples.
Fig. 6 is a photograph of an energy storage fabric obtained by co-spinning a fibrous aqueous secondary battery and cotton yarn in example.
Detailed Description
The following description is given for the purpose of illustration and to aid in the understanding of the invention, and it is to be understood that the invention is not limited to the details of the embodiments, which are set forth in the description and are not intended to limit the scope of the invention.
Fig. 1 is a schematic view of a process for integrally producing a fibrous aqueous secondary battery according to the present invention.
Examples
1. Design of multi-hole multifilament spinneret
Each module unit in the spinneret consists of two parallel inner channels of identical diameter and an outer channel containing the entire parallel inner channel, as shown in fig. 2. Wherein two parallel inner channels are used to achieve extrusion of the electrode slurry and an outer channel comprising the entire parallel channels is used to achieve extrusion of the water-based gel electrolyte. The inner diameter of the outer channel is 1-2.5 mm, and the distance between the outer walls of the two inner channels in each single spinning nozzle is equal to the distance between the outer walls of the inner channels and the inner walls of the outer channels along the diameter direction; meanwhile, the radius ratio of the inner channel to the outer channel is 1/5-2/5.
2. Preparation of electrode slurry
Firstly, the polyacrylate LA33 of the binder 1 or sodium carboxymethylcellulose is dissolved in a certain amount of water by using a high-speed dispersion machine. Then adding carbon nano tube and/or graphene aqueous slurry, metal nano particles stably dispersed in water, a metal oxide/polyanionic compound nano electrode material and a binder 2, namely styrene butadiene rubber or polytetrafluoroethylene emulsion in sequence, uniformly stirring, and performing vacuum defoaming to control the viscosity of the electrode slurry to be 12000-20000 mPa.s. The solid content of the electrode slurry is 20-40%, wherein the content of the binder is 3-12 wt%; the content of the carbon nano tube conductive agent is 30-65%, the content of the graphene conductive agent is 0-5%, and the content of the metal particle nano Cu or nano Ag is 0-7wt%; the content of the anode material or the cathode material is 20-50wt%; the raw materials used herein may be commercial products.
3. Preparation of aqueous gel electrolyte spinning solution
The polymer matrix of the water system gel electrolyte can be one or more of chitosan, polyvinyl alcohol, sodium alginate and sodium carboxymethylcellulose; the electrolyte salt is one or more of lithium perchlorate, lithium chloride, lithium sulfate and lithium nitrate. The polymer gel solution can be prepared first and then the electrolyte salt is added, or the high molecular polymer matrix and the electrolyte salt can be stirred and dissolved simultaneously to obtain the spinning solution, and the polymer is required to be swelled and then dissolved before the solution is prepared.
4. Integrated continuous construction of fibrous aqueous secondary battery
The polymer aqueous gel electrolyte spinning solution and the electrode slurry are extruded into the coagulation bath simultaneously by using a designed porous multifilament spinneret, wherein two parallel channels in the spinneret assembly unit are filled with the electrode slurry, and the outer channel is filled with the gel electrolyte spinning solution. A device structure is formed in which the two fiber electrodes are wrapped with a gel electrolyte immediately after encountering the coagulation bath, where the gel electrolyte simultaneously functions as a separator. The relative extrusion speed of the gel electrolyte spinning solution and the electrode slurry is controlled to be 1/0.05-1/0.5, the energy storage capacity and the structural stability of the fiber device are guaranteed, and when the relative extrusion speed ratio of the gel electrolyte spinning solution to the electrode slurry is 1/0.2 and the flow rate of the gel electrolyte is 16 mL/min, the structure of the fibrous lithium ion battery is shown in figure 3.
5. The multistage drafting technology is adopted to improve the degree of orientation of the carbon nano tube, and the post-drafting treatment technology can ensure that the mechanical property of a fiber device meets various processing requirements of the textile industry and simultaneously improve the conductivity of the nano tube. The mechanical strength of the fibrous water system secondary battery can be controlled to be 120 MPa at most by controlling the drawing ratio of the fiber device to be 1-10 times.
The integrated fibrous water system secondary battery construction method has a fast and stable production process, and when the relative extrusion speed ratio of the gel electrolyte spinning solution and the electrode slurry is 1/0.2 and the flow rate of the gel electrolyte spinning solution is 40mL/min, the production speed of a single multi-core spinneret orifice of the multi-orifice spinneret plate can reach more than 250m/h (as shown in figure 4). The fibrous aqueous lithium ion secondary battery with lithium manganate as a positive electrode active material, lithium titanium phosphate as a negative electrode active material, chitosan/polyvinyl alcohol/lithium sulfate as a gel electrolyte and a draft ratio of 1/5 has small specific capacity fluctuation along with the increase of production speed, and when the production rate is 50-250 m/h, the specific capacity is between 90-110 mAh/g. When the extrusion rate is 150 m/h, the specific capacity of the fibrous water-based lithium ion battery is the maximum and can reach 110mAh/g.
The integrated fibrous water-based secondary battery construction method is suitable for continuous preparation of various fibrous water-based secondary batteries, sodium manganate and sodium titanium phosphate are respectively used as positive and negative electrode materials of a sodium ion battery, nano zinc and manganese dioxide are used as positive and negative electrode materials of a zinc ion battery, and the fibrous water-based sodium ion secondary battery and the fibrous water-based zinc ion secondary battery can also be integrally prepared. Under the conditions that the relative extrusion speed ratio of the gel electrolyte spinning solution and the electrode slurry was 1/0.2, the fiber production rate was 100 m/h, and the draw-down ratio was 1/5, the capacity of each of the three fibrous aqueous batteries separately prepared could be maintained at 90% or more after fifty cycles (as shown in fig. 5).
The fibrous water-based secondary battery prepared by the integrated fibrous water-based secondary battery construction method can be co-spun with cotton yarns through a textile machine to obtain a large-area energy storage fabric (shown in figure 6), has the characteristics of flexibility, light weight and air and moisture permeability, can regulate and control the output voltage and current through a series-parallel connection design, realizes power supply for various wearable electronic devices, and has a wide application prospect in the field of wearable electronics.
Reference to the literature
[1] Simon, P.; Gogotsi, Y.; Dunn, B. Science 2014, 343, 1210-1211.
[2] Zhou, G.; Li, F.; Cheng, H. Energy Environ. Sci. 2014, 7, 1307-1338.
[3] Wang, L.; Feng, X.; Ren, L.; Piao, Q.; Zhong, J.; Wang, Y.; Li, H.; Chen, Y.; Wang, B. J.
Am. Chem. Soc. 2015, 137, 4920-4923.
[4] Ren, J.; Li, L.; Chen, C.; Chen, X.; Cai, Z.; Qiu, L.; Wang, Y.; Zhu, X.; Peng, H. Adv. Mater. 2013, 25, 1155-1159.
[5] Lima, M. D.; Fang, S.; Lepró, X.; Lewis, C.; Baughman, R. H.Science2011, 341, 51-55.
[6] ZhangY.; BaiW.; RenJ.; Weng W.; LinH.; ZhangZ.; PengH. J. Mater. Chem. A 2015, 3, 17553-17557.
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Claims (10)

1. An integrated industrial-grade preparation method of a fibrous water-system secondary battery is characterized by comprising the following specific steps:
(1) Preparing electrode slurry: mechanically stirring a polymer binder, a carbon nano conductive material, a metal particle conductive agent and an electrode active material according to a certain proportion to obtain spinnable electrode slurry, wherein the positive electrode slurry and the negative electrode slurry are different in electrode active material and consistent in formula of other components;
(2) Preparing a water-based gel electrolyte spinning solution: dissolving lithium salt in a polymer high molecular water solution to obtain a water system gel electrolyte spinning solution with certain viscosity;
(3) Integrated continuous construction: the method comprises the following steps of (1) simultaneously extruding positive electrode slurry, negative electrode slurry and a water system gel electrolyte spinning solution into a coagulating bath by using a porous composite spinneret plate, simultaneously forming a gel electrolyte and two fiber electrodes by using the coagulating bath, and simultaneously playing a role of a diaphragm by using the gel electrolyte so as to realize the integrated continuous preparation of the fibrous water system secondary battery; wherein each component unit in the porous composite spinneret plate consists of two identical parallel inner channels and an outer channel containing the parallel inner channels; the two parallel inner channels are used for realizing the extrusion molding of the electrode slurry, and the outer channel comprising the two parallel channels is used for realizing the extrusion molding of the water-based gel electrolyte;
(4) Post-drafting treatment: drafting the formed fibrous water system secondary battery sample by a continuous multi-stage drafting technology;
(5) Drying and packaging: the drafted fibrous water system secondary battery sample is washed for multiple times and then is partially dried, and then continuous coating is used for packaging the partially dried fibrous water system secondary battery sample on line, so that the fibrous water system secondary battery is obtained.
2. The integrated industrial-scale preparation method of claim 1, wherein in the step (1), the polymer binder is selected from one or more of carboxymethyl cellulose, sodium alginate, polyacrylate, polyethylene glycol, styrene butadiene rubber or polytetrafluoroethylene; the carbon nano conductive material is a carbon nano tube and graphene; the metal particle conductive agent is selected from one of nano silver or nano copper; the positive electrode material is selected from metal oxideObject MnO 2 、LiMnO 2 、Na 0.44 MnO 2 Or polyanionic compounds LiFePO 4 One of (1); the negative electrode material is selected from metal oxide TiO 2 、 Li 4 Ti 5 O 12 Or polyanionic compound LiTi 2 (PO 4 ) 3 、NaTi 2 (PO 4 ) 3 Or metal particle nano zinc.
3. The integrated industrial-scale production method of claim 2, wherein in the step (1), the polymer binder content is 3-12 wt% based on 100% of the total solids in the electrode slurry; the content of the carbon nano tube is 30-65wt%, and the content of the graphene is 0-5wt%; the content of the metal particle conductive agent is 0-7wt%; the content of the positive electrode material or the negative electrode material is independently 20 to 50wt%.
4. The integrated industrial-scale preparation method of claim 1, wherein in the step (1), the solvent in the electrode slurry is water, the solid content of the electrode slurry is 20-40wt%, and the viscosity of the electrode slurry is 12000-20000 mPa.s.
5. The integrated industrial-grade preparation method of claim 1, wherein in the step (2), the polymer is selected from one or more of chitosan, polyvinyl alcohol, sodium alginate, sodium carboxymethylcellulose or polyethylene glycol; the lithium salt is selected from one or more of lithium perchlorate, lithium chloride, lithium sulfate or lithium nitrate.
6. The integrated industrial-scale production method according to claim 1, wherein in the step (2), the viscosity of the aqueous gel electrolyte spinning solution is 6000 to 11000 mpa.s.
7. The integrated industrial-scale preparation method of claim 1, wherein in the step (3), the inner diameter of the outer channel of each module unit in the porous composite spinneret plate is 1-2.5 mm, the distance between the outer walls of the two parallel inner channels is kept equal to the distance between the outer walls of the inner channels and the inner walls of the outer channels in the diameter direction, and the diameter ratio of the inner and outer channels is 1/5-2/5.
8. The integrated, industrial-scale production process of claim 1, wherein in step (3), the relative extrusion rate of the aqueous gel electrolyte dope and the electrode slurry is 1/0.05 to 1/0.5.
9. The integrated industrial-grade production method according to claim 1, wherein in the step (4), the draft magnification is 1 to 10 times.
10. The integrated industrial-scale preparation method according to claim 1, wherein in the step (5), the moisture in the hydrogel fiber of the fiber-water-based secondary battery is partially dried by air-blast drying, the water content is controlled to be 30 wt% -60 wt%, and the diameter of the fiber-water-based secondary battery is controlled to be 200-600 μm; and performing in-situ continuous online packaging on the fiber water system secondary battery by using one or more of polyurethane packaging glue, PEFE emulsion and PVDF emulsion, wherein the diameter of the packaged fiber water system secondary battery is 400-800 μm.
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