CN106876773A - Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector - Google Patents

Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector Download PDF

Info

Publication number
CN106876773A
CN106876773A CN201710140078.7A CN201710140078A CN106876773A CN 106876773 A CN106876773 A CN 106876773A CN 201710140078 A CN201710140078 A CN 201710140078A CN 106876773 A CN106876773 A CN 106876773A
Authority
CN
China
Prior art keywords
graphite paper
aniline
collector
zinc
secondary cell
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.)
Pending
Application number
CN201710140078.7A
Other languages
Chinese (zh)
Inventor
阚锦晴
胡转
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.)
Yangzhou University
Original Assignee
Yangzhou University
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 Yangzhou University filed Critical Yangzhou University
Priority to CN201710140078.7A priority Critical patent/CN106876773A/en
Publication of CN106876773A publication Critical patent/CN106876773A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector, is related to the collector technical field of secondary cell, and its negative electrode is the aniline and 5 aminosalicyclic acid copolymers being supported on frivolous graphite paper, and anode is zinc metal sheet.Collector of the invention is frivolous graphite paper, frivolous graphite paper good conductivity, there is that certain mechanical strength and corrosion resistance are strong, and material internal resistance is almost nil, low cost, and pliability is good, is easy to cut and processes.Charge/discharge capacity change of the secondary cell for preparing in the process of the present invention under different current densities is little, is adapted to discharge and recharge under high current, and specific discharge capacity is high, and cyclicity is good.

Description

Graphite paper is the zinc/aniline and 5-aminosalicylic acid copolymer secondary cell of collector
Technical field
The present invention relates to the collector technical field of secondary cell.
Technical background
Growing and social and sustainable economic development continuous improvement with people to energy demand, with height The green energy resource of performance low cost causes the original more concerns of people.Polyaniline is used as a kind of most promising conducting polymer Thing material is due to good electric conductivity, with low cost, simple being readily synthesized and be easy in the aqueous solution and air system The advantages of synthesis.Therefore, polyaniline will be the promising active material that can fill secondary cell.
Zinc/Polyaniline Cell has been reported, and has important breakthrough.However, nowadays developing one that Polyaniline Cell meets with Major issue is exactly the stability of collector.The collector of Polyaniline Cell should meet following condition：The good conductor of electric charge, foot Enough mechanical strengths, corrosion resistance, chemistry and electrochemical stability.Once there is corrosion or dissolve, active matter in collector Contact resistance between matter and collector will increase.In addition, the metal ion of dissolving will pollute electrolyte.These factors all can Cause the decline of battery performance.At present, usually using platinum, gold, CNT etc. as Polyaniline Cell collector.Although this A little materials can meet conditions above, but their either expensive or machine-shapings are difficult.And conventional material such as aluminium Paper tinsel, Copper Foil, nickel foil and stainless steel are not suitable for Polyaniline Cell yet.Therefore, the commercialization of Polyaniline Cell is realized, it is necessary to seek A kind of suitable collector.
Zinc/aniline is mainly made up of with 5-aminosalicylic acid copolymer secondary cell four parts：Negative electrode, anode, electrolysis Matter and barrier film., used as negative electrode, zinc metal sheet is used as anode for aniline polymer.Its operation principle is using conduction high polymer aniline polymer Doping realizes redox reaction with the invertibity of dedoping in charge and discharge process.
The content of the invention
Capacity the present invention be directed to existing zinc/Polyaniline Secondary Battery is low, the short intrinsic problem of grade of cycle life, proposes one Plant the Water-Electrolyte zinc/aniline and 5-aminosalicylic acid copolymer secondary cell for making collector with graphite paper.
The negative electrode of secondary cell of the present invention is the aniline and 5-aminosalicylic acid copolymer being supported on frivolous graphite paper, sun Extremely zinc metal sheet.
Electrolyte of the present invention is ZnCl that pH value is 4.0~6.02、NH4The mixed solution of Cl and acylate composition.
Collector of the invention is frivolous graphite paper, frivolous graphite paper good conductivity, there is certain mechanical strength and anti- Corrosive nature is strong, and material internal resistance is almost nil, low cost, and pliability is good, is easy to cut and processes.
According to battery charging and discharging result, the specific discharge capacity of copolymer battery is 145 mAhg-1, battery is under constant current Continuous discharge and recharge 150 times, the specific discharge capacity of the 150th time is 96 mAhg-1, coulombic efficiency is 97%.Zinc/aniline of the invention There is good charge-discharge performance with 5-aminosalicylic acid copolymer secondary cell.By further research, it is possible to turn into Heavy-duty battery of future generation.
Further, the electrolyte of secondary cell of the present invention is by 1.0~3.0 M ZnCl2, 2.0~4.0 M NH4Cl and have The aqueous solution of machine hydrochlorate composition, the pH of electrolyte is 4.0~6.0.The mixed solution is to aniline and 5-aminosalicylic acid copolymer Chemical property have not significant impact, can effectively suppress the formation of the gas-evolving electrodes and zinc dendrite of zinc electrode.
In addition, the acylate is acetate, propionate, butyrate, caprylate, adipate, malonate, fourth two Hydrochlorate, maleate, tartrate, benzoate, phenylacetate, phthalate, valerate, caproate, caprate, third One or more in olefin(e) acid salt or citrate.
Brief description of the drawings
Fig. 1 is the structural representation of secondary cell of the present invention.
Fig. 2 is cyclic voltammogram of the blank graphite paper collector in different pH value.
Fig. 3 is AC impedance figure of the blank graphite paper collector in different pH value.
Fig. 4 be zinc/aniline from 5-aminosalicylic acid copolymer secondary cell different current densities constant current charge-discharge Curve.
Fig. 5 is charging and discharging curve of the zinc/aniline from 5-aminosalicylic acid copolymer secondary cell in different cycle-indexes.
Specific implementation method
First, secondary cell is prepared：
1st, the preparation of positive pole：
（1）The preparation of electrolyte：
Raw material：Aniline, 5-aminosalicylic acid, hydrochloric acid and redistilled water.Wherein, aniline is stored in low temperature bar after vacuum distillation It is standby under part.
Configuration 100mL contents are respectively the 5-aminosalicylic acid of the aniline of 0.1~1.0mol/L, 0.01~0.1mol/L With the aqueous hydrochloric acid solution of 0.5~2.0 mol/L, it is uniform with magnetic stirrer.
（2）Collector：By graphite paper second distillation water washing, drying.Then 25 cm are cut into2Sheet, it is standby.
（3）The synthesis of aniline and 5-aminosalicylic acid copolymer：The electrolyte that will be prepared is placed in three pipe electrolytic cells, with The back side scribbles the frivolous graphite paper of sheet of insulating barrier for working electrode, with saturated calomel electrode as reference electrode, platinum electrode be right Electrode, is 0.7~1.5 V in current potential using constant potential electrochemical polymerization（Relative to saturated calomel electrode）Under conditions of Electrochemistry formated 5~20 minutes, makes flake graphite paper area load have 0.01~1g aniline and 5-aminosalicylic acid copolymer.
The frivolous graphite paper second distillation water washing of sheet of aniline and 5-aminosalicylic acid copolymer will be loaded with, then 24 more than h are vacuum dried in 70~90 DEG C of baking oven again.
2nd, the preparation of negative pole：
The purity of zinc metal sheet is 99.99%, and thickness is 0.010~0.25mm, is cut to 25cm2Sheet, with abrasive paper for metallograph polish go Fall oxide on surface, then use secondary water washing, dry, preserve under anaerobic stand-by.
3rd, the preparation of zinc-aniline and 5-aminosalicylic acid copolymer secondary cell electrolyte：
By ZnCl2The NH of sum4Cl is dissolved in secondary water, is configured to containing 1.0~3.0 M ZnCl2With 2.0~4.0 M NH4The mixed solution of Cl, and concentration is added for 0.01~0.5M acylates, then the pH of solution is adjusted with hydrochloric acid or NaOH It is worth 4.0~6.0.
Wherein acylate is selected from acetate, propionate, butyrate, caprylate, adipate, malonate, succinic acid Salt, maleate, tartrate, benzoate, phenylacetate, phthalate, valerate, caproate, caprate, propylene The combination of one or more in hydrochlorate, citrate.
4th, the assembling of battery：
Successively by zinc metal sheet, with the barrier film for separating battery plus-negative plate effect（Such as polypropylene non-woven fabric）With load aniline and 5- amino The graphite paper of salicylic acid copolymers is stacked together in order, and is tightened with insulating materials, is put into container, adds appropriate preparation Good battery electrolyte, is assembled into secondary cell.Structural representation such as Fig. 1.
The open-circuit voltage of the secondary cell of assembling is 1.3 ± 0.2V, battery discharge and recharge between 0.7~1.5 V.Copolymerization The specific discharge capacity of thing battery is 145 mAhg-1, battery continuous discharge and recharge 150 times under constant current, the electric discharge ratio of the 150th time Capacity is 96 mAhg-1, coulombic efficiency is 97%.
2nd, performance test：
The present invention uses Series Electrochemical method such as cyclic voltammetric, electrochemical AC impedance, charge-discharge test to study collector Electrochemical properties, and polymer secondary battery charge-discharge performance.
1st, cyclic voltammetry curve of the blank graphite paper under the electrolyte conditions of different pH：
Using with above secondary cell identical electrolyte, with blank graphite paper as positive pole, with zinc metal sheet as negative pole, using circulation lie prostrate Peace is tested, and obtains the cyclic voltammetry curve under the different pH shown in Fig. 2.
In Fig. 2, curve a is the cyclic voltammetry curve under graphite paper is 4.20 in pH value.Curve b is that graphite paper is in pH value Cyclic voltammetry curve under 4.70.Curve c is the cyclic voltammetry curve under graphite paper is 5.20 in pH value.
It can be seen that the stable chemical nature of graphite paper.
2nd, AC impedance curve of the blank graphite paper under the electrolyte conditions of different pH：
Using with above secondary cell identical electrolyte, with blank graphite paper as positive pole, with zinc metal sheet as negative pole, using circulation lie prostrate Peace is tested, and obtains the AC impedance curve under the different pH shown in Fig. 3.
In Fig. 3, curve a is the AC impedance curve under graphite paper is 4.20 in pH value.Curve b is that graphite paper is in pH value AC impedance curve under 4.70.Curve c is the AC impedance curve under graphite paper is 5.20 in pH value.
It can be seen that the electric charge transfer internal resistance of graphite paper is substantially zeroed.
3rd, constant current charge-discharge curve of the secondary cell in different current densities：
The constant current charge-discharge experiment under different current densities is carried out to secondary cell prepared by the present invention, as shown in Figure 4.
In Fig. 4, curve a is that copolymer battery is 117 mAg in current density-1Under charging and discharging curve.Curve b is altogether Polymers battery is 78 mAg in current density-1Under charging and discharging curve.Curve c is that copolymer battery is 39 in current density mA·g-1Under charging and discharging curve.
Shown according to test result：The charge/discharge capacity change of secondary cell prepared by the present invention under different current densities Less, show that the battery is adapted to discharge and recharge under high current.
4th, charging and discharging curve of the secondary cell in different cycle-indexes：
Charge and discharge electric test during different cycle-indexes is carried out to secondary cell prepared by the present invention, as a result as shown in Figure 5.
In Fig. 5, curve a is that copolymer battery is 78mAg in current density-1When discharge and recharge number of times be 50thWhen charge and discharge Electric curve.Curve b is that copolymer battery is 78mAg in current density-1When discharge and recharge number of times be 100thWhen discharge and recharge it is bent Line.Curve c is that copolymer battery is 78mAg in current density-1When discharge and recharge number of times be 150thWhen charging and discharging curve.
It can be seen that secondary cell specific discharge capacity prepared by the present invention is high, cyclicity is good.

Claims (3)

1. graphite paper is the zinc/aniline and 5-aminosalicylic acid copolymer secondary cell of collector, it is characterised in that negative electrode is negative Aniline and 5-aminosalicylic acid copolymer on frivolous graphite paper are loaded in, anode is zinc metal sheet.
2. graphite paper described in claim 1 is the zinc/aniline and 5-aminosalicylic acid copolymer secondary cell, its feature of collector It is：The electrolyte of the secondary cell is by 1.0~3.0 M ZnCl2, 2.0~4.0 M NH4The water of Cl and acylate composition Solution, the pH of electrolyte is 4.0~6.0.
3. graphite paper described in claim 2 is the zinc/aniline and 5-aminosalicylic acid copolymer secondary cell, its feature of collector It is：The acylate is acetate, propionate, butyrate, caprylate, adipate, malonate, succinate, horse Come hydrochlorate, tartrate, benzoate, phenylacetate, phthalate, valerate, caproate, caprate, acrylates Or one or more in citrate.
CN201710140078.7A 2017-03-10 2017-03-10 Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector Pending CN106876773A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710140078.7A CN106876773A (en) 2017-03-10 2017-03-10 Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710140078.7A CN106876773A (en) 2017-03-10 2017-03-10 Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector

Publications (1)

Publication Number Publication Date
CN106876773A true CN106876773A (en) 2017-06-20

Family

ID=59170020

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710140078.7A Pending CN106876773A (en) 2017-03-10 2017-03-10 Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector

Country Status (1)

Country Link
CN (1) CN106876773A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104241657A (en) * 2014-09-30 2014-12-24 扬州大学 Current collector material of polyaniline battery and battery using same
CN104882631A (en) * 2015-05-05 2015-09-02 哈尔滨天宝石墨科技发展有限公司 Method for improving uniform heat dispersion performance of lithium ion battery electrode piece
CN105111434A (en) * 2015-10-10 2015-12-02 扬州大学 Aniline copolymer and graphene composite as well as preparation method and application thereof
CN105924643A (en) * 2016-06-17 2016-09-07 江苏科技大学 Electrochemical preparation method of phenylamine-4-aminosalicylic acid copolymer
CN106083623A (en) * 2016-06-08 2016-11-09 黑龙江鑫创生物科技开发有限公司 A kind of preparation method of 5 aminosallcylic acids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104241657A (en) * 2014-09-30 2014-12-24 扬州大学 Current collector material of polyaniline battery and battery using same
CN104882631A (en) * 2015-05-05 2015-09-02 哈尔滨天宝石墨科技发展有限公司 Method for improving uniform heat dispersion performance of lithium ion battery electrode piece
CN105111434A (en) * 2015-10-10 2015-12-02 扬州大学 Aniline copolymer and graphene composite as well as preparation method and application thereof
CN106083623A (en) * 2016-06-08 2016-11-09 黑龙江鑫创生物科技开发有限公司 A kind of preparation method of 5 aminosallcylic acids
CN105924643A (en) * 2016-06-17 2016-09-07 江苏科技大学 Electrochemical preparation method of phenylamine-4-aminosalicylic acid copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHAOLIN MU，QIAOFANG SHI: "Controllable preparation of poly(aniline-co-5-aminosalicylic acid) nanowires for rechargeable batteries", 《SYNTHETIC METALS》 *

Similar Documents

Publication Publication Date Title
Chen et al. Electrochemical properties of poly (aniline-co-N-methylthionine) for zinc-conducting polymer rechargeable batteries
CN106340616A (en) Lithium cathode used for lithium battery and provided with sandwich structure and preparation method thereof
CN111293287B (en) Lithium metal negative electrode and preparation and application thereof
CN102903917B (en) Aqueous electrolyte rechargeable zinc ion battery
TW522580B (en) Secondary battery of proton conductive polymer
CN108447696A (en) A kind of preparation method and applications of polypyrrole/conduction carbon cloth combination electrode
Liu et al. A high-voltage aqueous rechargeable zinc-polyaniline hybrid battery achieved by decoupling alkali–acid electrolyte
CN102274965B (en) Method for improving electrochemical performance of hydrogen storage alloy powder by utilizing electropolymerization polyaniline
CN104241657A (en) Current collector material of polyaniline battery and battery using same
Ke et al. Hydroquinone-based conjugated Schiff base polymer as anode material for lithium ion batteries
CN104466122A (en) Method for preparing nickel positive electrode of nickel-metal hydride secondary battery by using cobalt-aluminum hydrotalcite and application thereof
Mu et al. Controllable preparation of poly (aniline-co-5-aminosalicylic acid) nanowires for rechargeable batteries
TWI246222B (en) Electrochemical cell
CN107845778B (en) Method for modifying lead storage battery positive plate by polyaniline
Mengoli et al. Studies of Zn| ZnX 2| polyaniline batteries. II. X= I
CN106876773A (en) Graphite paper is the zinc/aniline and 5 aminosalicyclic acid copolymer secondary cells of collector
CN106058258B (en) A kind of polymer lead-acid accumulator
CN114784284A (en) Zinc anode modified by silk fibroin coating, preparation method and application thereof
CN114243019A (en) Zinc cathode material with double modification layers on surface, preparation method thereof and application of zinc cathode material in water-based zinc ion battery
CN114249860A (en) Preparation and application of water-system zinc ion battery gel electrolyte
CN101179139A (en) Novel polymer lithium ion battery with polyindole as cathode
Hu et al. Effect of electrolyte composition on zn electrode in weak acidic aqueous electrolyte
US20230144715A1 (en) Eutectic electrolyte for the zinc based rechargeable redox static energy storage devices
Shaolin et al. Poly-o-methylaniline used as a cathode material in rechargeable batteries
Changzhi et al. A wound-type lithium/polyaniline secondary cell

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170620

WD01 Invention patent application deemed withdrawn after publication