CN112786894B - Biodegradable secondary fiber battery and preparation method thereof - Google Patents

Biodegradable secondary fiber battery and preparation method thereof Download PDF

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CN112786894B
CN112786894B CN202110078050.1A CN202110078050A CN112786894B CN 112786894 B CN112786894 B CN 112786894B CN 202110078050 A CN202110078050 A CN 202110078050A CN 112786894 B CN112786894 B CN 112786894B
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biodegradable
fiber
battery
conductive
electrode
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CN112786894A (en
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彭慧胜
梅腾龙
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • 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
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • 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
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Abstract

The invention belongs to the technical field of energy storage devices, and particularly relates to a biodegradable secondary fiber battery and a preparation method thereof. The invention firstly prepares biodegradable conductive fiber, then uses the conductive fiber as a substrate, respectively compounds anode and cathode electrode materials to obtain fiber electrodes, coats a layer of biodegradable polymer gel on the outer surface of a certain fiber electrode as a diaphragm, and finally twists the anode and the cathode of the fiber to obtain the integrated biodegradable secondary fiber battery. The fiber battery can be implanted into a body in an injection mode, and can be normally charged and discharged by taking body fluid as electrolyte. After completion of the required work task, the fiber battery can be gradually degraded in body fluids without surgical removal, and is expected to power biodegradable medical electronics.

Description

Biodegradable secondary fiber battery and preparation method thereof
Technical Field
The invention belongs to the technical field of energy storage devices, and particularly relates to a biodegradable secondary fiber battery and a preparation method thereof.
Background
Biodegradable electronic devices have great application prospects in the field of medical health, and attract great research interests of researchers. However, as a source of energy supply for biodegradable electronic devices, the development of biodegradable energy systems has been a great challenge to date. Most of the existing biodegradable energy systems are rigid block-shaped metal primary batteries, and the requirements of in-vivo application are difficult to meet due to the high modulus and serious side reactions of the existing biodegradable energy systems, so that the clinical application of biodegradable electronic devices is severely restricted. Therefore, it is very important to develop a novel biodegradable battery with miniaturization, flexibility and safety, which is expected to provide a suitable energy solution for biodegradable electronic devices.
Disclosure of Invention
The invention aims to provide a biodegradable secondary fiber battery and a preparation method thereof.
The invention provides a biodegradable secondary fiber battery, which consists of a biodegradable fiber electrode and a diaphragm; the fiber electrode is obtained by respectively compounding anode and cathode electrode materials by using biodegradable conductive fibers as a substrate.
In the invention, the biodegradable conductive fiber is one of degradable conductive polymers (such as polyphosphazene, block copolymers of polylactic acid and aniline oligomers, and the like) and composites of the degradable polymers and conductive materials (such as blends of polylactic acid and nano carbon black, silk fibroin surface modified polypyrrole, polylactic acid surface iron-plated film, polyglycolic acid surface gold-plated film, and the like).
In the invention, the anode material is one or a composite of more of manganese dioxide, ruthenium dioxide, vanadium pentoxide, polyanion compounds and Prussian blue analogues, and the cathode material is one or a composite of more of activated carbon, molybdenum trioxide, phosphate, polyimide, polydopamine and polypyrrole.
In the invention, the biodegradable diaphragm is one or a composite of several of chitosan, hyaluronic acid, alginic acid, heparin, gelatin, fibrin, polypeptide and polyethylene glycol-polylactic acid block copolymer.
The invention provides a preparation method of a biodegradable secondary fiber battery, which comprises the following specific steps:
(1) And preparing the biodegradable conductive fiber. Plating a layer of metal film with the thickness of 80 nm-150 nm (preferably 100 nm) on the outer surface of the degradable polymer fiber by chemical synthesis or an ion sputtering coating instrument to obtain the biodegradable conductive fiber;
(2) And preparing the biodegradable fiber electrode. Respectively compounding positive and negative electrode materials by using biodegradable conductive fibers as a substrate through in-situ polymerization, electrodeposition and other modes to obtain positive and negative fiber electrodes;
(3) And (3) preparing a biodegradable secondary fiber battery. Coating a layer of biodegradable polymer gel on the outer surface of a certain fiber electrode by means of dip coating and the like to be used as a diaphragm, and twisting the positive and negative fiber electrodes to obtain the integrated biodegradable secondary fiber battery.
The traditional biodegradable battery adopts a metal sheet as an electrode, and the high modulus and serious side reaction of the traditional biodegradable battery make the traditional biodegradable battery difficult to meet the requirements of in-vivo application. The biodegradable secondary fiber battery provided by the invention consists of a biodegradable fiber electrode and a diaphragm. Due to the one-dimensional configuration and excellent flexibility, the fiber battery can be implanted into the body in an injection mode, and body fluid can be used as electrolyte to be charged and discharged normally. After completion of the required work task, the fiber battery can be gradually degraded in body fluids without surgical removal, and is expected to power biodegradable medical electronics.
Drawings
Fig. 1 is a scanning electron microscope photograph of the biodegradable conductive fiber in the example.
Fig. 2 is a structural representation of a biodegradable fiber negative electrode in an example. Wherein, a and b are scanning electron microscope pictures of the cathode under low power and high power respectively.
Fig. 3 is a structural representation of the biodegradable fiber positive electrode in the examples. Wherein, a and b are respectively scanning electron microscope photographs of the positive electrode under low power and high power.
Fig. 4 is a scanning electron microscope photograph of the biodegradable secondary fiber battery in the example.
FIG. 5 is a 1000 mA.g external view of the biodegradable secondary fiber battery in the example -1 Charge and discharge curves at current density.
Fig. 6 is a characterization of the degradation process of the biodegradable secondary fiber battery in vitro in the examples.
Fig. 7 is a schematic diagram of the injection implantation process, in vivo working process and in vivo degradation process after use of the biodegradable secondary fiber battery in the embodiment.
FIG. 8 shows in vivo 1000 mA g of the biodegradable secondary fiber battery in the example -1 Charge and discharge curves at current density.
Fig. 9 is a characterization of the degradation process of the biodegradable secondary fiber battery in vivo in the examples.
Detailed Description
The present invention is further described with reference to specific examples, but the specific details of the examples are only for illustrating the present invention and do not represent all technical solutions conceived by the present invention, therefore, should not be construed as limiting the general technical solutions of the present invention, and some insubstantial additions and modifications, such as simple changes or substitutions with technical features having the same or similar effects, which are seen by a skilled person, are included in the scope of the present invention.
(1) And preparing the biodegradable conductive fiber. And arranging the polyglycolic acid yarn on a glass sheet, placing the glass sheet in a cavity of an ion sputtering gilding instrument, and carrying out gilding treatment on the glass sheet, wherein the sputtering current is set to be 10 mA, and the sputtering time is set to be 15 min. After the gold plating process is completed, a plurality of gold-plated polyglycolic acid yarns are twisted to obtain biodegradable conductive fibers (fig. 1).
(2) And preparing the biodegradable fiber negative electrode. Preparing 5g/L dopamine hydrochloride solution by using Tris-HCl buffer solution with the pH value of 8.5 as a solvent. Immersing the biodegradable conductive fiber in the reaction solution, and polymerizing in situ in the air at 60 ℃ for 24 h. After the polymerization reaction is finished, the obtained composite fiber is immersed in polypyrrole electroplating solution (0.1M pyrrole, 0.1M potassium nitrate and pH of 3) as a working electrode, a platinum sheet is used as a counter electrode, saturated calomel is used as a reference electrode, polypyrrole is electroplated under a constant potential of 0.7V, the mass ratio of polydopamine to polypyrrole is controlled to be 1.
(3) And preparing the biodegradable fiber positive electrode. In order to ensure the consistency of the degradation rates of the two fiber electrodes, the conductive fibers for preparing the fiber positive electrode are soaked in a Tris-HCl buffer solution with the pH value of 8.5 for 24 hours at the temperature of 60 ℃. The treated conductive fibers were immersed in a manganese dioxide electroplating solution (0.1M manganese acetate, 0.1M sodium sulfate) as a working electrode, and manganese dioxide was electroplated cyclically at 1.5V 1s and 0.7V 10 s using a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode. After the electroplating, the anode was washed with deionized water and dried at room temperature to obtain a biodegradable fiber anode (fig. 3).
(4) And (3) preparing a biodegradable secondary fiber battery. The outer surface of the fiber anode is coated with a layer of degradable chitosan hydrogel (4 wt%) by a dip coating method, and the degradable chitosan hydrogel is twisted with the fiber anode after being dried at room temperature, so that the final biodegradable secondary fiber battery can be obtained (figure 4).
The prepared fiber battery can be normally charged and discharged in phosphate buffered saline solution (fig. 5), and can be gradually degraded in phosphate buffered saline solution at 37 ℃ (fig. 6). Due to the one-dimensional configuration and the excellent flexibility, the fiber battery can be implanted into the body in an injection mode, and body fluid can be used as electrolyte to be charged and discharged normally (figure 7). At 1000 mA · g -1 The fiber battery showed 25.6 mAh.g in vivo at a current density of -1 Specific capacity of (2) (fig. 8). After completion of the required work task, the fiber battery can be gradually degraded in body fluids without surgical removal (fig. 9).

Claims (2)

1. A biodegradable secondary fiber battery is characterized by consisting of a biodegradable fiber electrode and a diaphragm; the fiber electrode is obtained by respectively compounding anode and cathode electrode materials by using biodegradable conductive fibers as a substrate; wherein the biodegradable conductive fiber is one of a degradable conductive polymer and a composite of the degradable polymer and a conductive material; wherein:
the degradable conductive polymer is selected from block copolymers of polyphosphazene, polylactic acid and aniline oligomers;
the compound of the degradable polymer and the conductive material is selected from a blend of polylactic acid and nano carbon black, silk fibroin surface modified polypyrrole, a polylactic acid surface iron-plated film and a polyglycolic acid surface gold-plated film;
the anode material is one or a composite of more of manganese dioxide, ruthenium dioxide, vanadium pentoxide, polyanion compounds and Prussian blue analogues;
the negative electrode material is one or a compound of more of activated carbon, molybdenum trioxide, phosphate, polyimide, polydopamine and polypyrrole;
the biodegradable diaphragm material is one or a composite of several of chitosan, hyaluronic acid, alginic acid, heparin, gelatin, fibrin, polypeptide and polyethylene glycol-polylactic acid block copolymer.
2. The method for preparing the biodegradable secondary fiber battery according to claim 1, comprising the steps of:
(1) Preparing biodegradable conductive fibers; plating a layer of metal film with the thickness of 80 nm-150 nm on the outer surface of the degradable polymer fiber by adopting chemical synthesis or an ion sputtering coating instrument to obtain the biodegradable conductive fiber;
(2) Preparing a biodegradable fiber electrode; respectively compounding positive and negative electrode materials by using biodegradable conductive fibers as a substrate in an in-situ polymerization and electrodeposition mode to obtain positive and negative fiber electrodes;
(3) Preparing a biodegradable secondary fiber battery; coating a layer of biodegradable polymer gel on the outer surface of a certain fiber electrode as a diaphragm, and twisting the positive and negative fiber electrodes to obtain the integrated biodegradable secondary fiber battery.
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Citations (1)

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CN1529653A (en) * 2001-05-16 2004-09-15 �й���ѧԺ���ݻ�ѧ�о��� Biodegradable and/or biological absorbing fiber product and its use in medical application

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DE112008000124T5 (en) * 2007-01-12 2010-02-11 Ofek Eshkolot Research And Development Ltd. Fibrous anode with high surface area / volume ratio for fuel cells and a fuel cell with such an anode
US8386031B2 (en) * 2009-06-30 2013-02-26 Boston Scientific Scimed, Inc. Implantable self-powered biodegradable medical device to treat or prevent reperfusion injury
FR2972439B1 (en) * 2011-03-07 2013-04-19 Commissariat Energie Atomique BIODEGRADABLE ELECTROCONDUCTIVE NANOFIL, PROCESS FOR PRODUCING THE SAME AND USES THEREOF
CN106374147A (en) * 2016-12-08 2017-02-01 复旦大学 Flexible water-based sodium-ion batteries and preparation method thereof
CN109979763B (en) * 2019-04-30 2021-07-16 中国科学院苏州纳米技术与纳米仿生研究所 Folding-resistant one-dimensional fibrous flexible energy storage device and preparation method thereof

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CN1529653A (en) * 2001-05-16 2004-09-15 �й���ѧԺ���ݻ�ѧ�о��� Biodegradable and/or biological absorbing fiber product and its use in medical application

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