CN106299288A - The application in chloride ion cell positive material of the polymer matrix composite of a kind of chlorine doping - Google Patents
The application in chloride ion cell positive material of the polymer matrix composite of a kind of chlorine doping Download PDFInfo
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- CN106299288A CN106299288A CN201610812191.0A CN201610812191A CN106299288A CN 106299288 A CN106299288 A CN 106299288A CN 201610812191 A CN201610812191 A CN 201610812191A CN 106299288 A CN106299288 A CN 106299288A
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- matrix composite
- polymer matrix
- polymer
- chlorine
- chloride ion
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000000460 chlorine Substances 0.000 title claims abstract description 38
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 229920013657 polymer matrix composite Polymers 0.000 title claims abstract description 23
- 239000011160 polymer matrix composite Substances 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 20
- 229920000128 polypyrrole Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical group CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 6
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 238000010670 acid alkali reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The present invention relates to the polymer matrix composite application in chloride ion cell positive material of a kind of chlorine doping.In the polymer matrix composite of above-mentioned chlorine doping, the quality of the polymer of chlorine doping accounts for the 50 100% of polymer matrix composite quality, and the quality of material with carbon element accounts for the 0 50% of polymer matrix composite quality.The polymer matrix composite of chlorine provided by the present invention doping can solve precipitation problem and the metal oxychloride positive electrode bigger change in volume problem in charge and discharge process of chloride ion battery metal chloride positive electrode, the cyclical stability of chloride ion cell positive material can be significantly improved, development high stable chloride ion battery is had important impetus.
Description
Technical field
The invention belongs to energy field, at chloride ion battery be just specifically related to the polymer matrix composite of a kind of chlorine doping
Application in the material of pole.
Background technology
Chloride ion battery is a kind of novel secondary battery based on cl anion conduction.This battery includes multiple electrode body
System, its theoretical energy density reaches 2500Wh/l, higher than traditional lithium ion battery.Have the Mg of high elemental abundance, Ca, Na,
FeCl3、CuCl2And MgCl2Can be as the electrode material of chloride ion battery Deng material.Although chloride ion battery have bigger from
Sub-radius, but also can show the high mobility of comparison and reaction reversibility.
In research in advance, chloride ion battery is by metal chloride/metal electrode system and the ion that can transmit chloride ion
Liquid electrolyte is constituted.Zhao et al. is at entitled " the Chloride ion of volume 245 of magazine Journal of Power Sources
Battery:a new member in the rechargeable family " in report that metal chloride positive pole can be with
Chloride ion generation lewis acid alkali reaction in electrolyte, causes electrode material precipitation, so that cell performance decay.Zhao etc.
People is at volume 52 51 phase entitled " Metal of magazine Angewandte Chemie Internatioanl Edition
Oxychlorides as cathode materials for chloride ion batteries " in report metal chlorine oxygen
Compound material has higher stability, it is possible to as chloride ion cell positive material, for solving metal chloride positive electrode
Precipitation problem bring significant contribution.But the change in volume (FeO/ that metal oxychloride is bigger during charge and discharge cycles
The theoretical volume of FeOCl is changed to 141.7%), the microstructure design of material is proposed the requirement that comparison is high.Visible, open
Send out novel, high stability chloride ion cell positive material is one of key point realizing chloride ion battery applications.
Summary of the invention
The invention aims to improve the precipitation problem of existing metal chloride positive pole and metal oxychloride relatively
Large volume variation issue, and provide polymer matrix composite that a kind of chlorine adulterates in chloride ion cell positive material should
With.
The technical scheme is that polymer matrix composite that a kind of chlorine adulterates is in chloride ion cell positive material
Application.In the polymer matrix composite of the most above-mentioned chlorine doping, the quality of the polymer of chlorine doping accounts for polymer base and is combined
The 50-100% of quality of materials, the quality of material with carbon element accounts for the 0-50% of polymer matrix composite quality.
The polymer of the most above-mentioned chlorine doping is chlorination polypyrrole, chlorinated polyphenyl amine or chlorination polythiophene.
The most above-mentioned material with carbon element is CNT, Graphene, carbon black, carbon fiber or porous carbon.
The polymer matrix composite of the most above-mentioned chlorine doping uses chemical reduction method to prepare, and specifically comprises the following steps that
A: polymer monomer pyrroles, aniline or the thiophene through distillation purifying is scattered in the deionized water through ice bath cooling
In, adding 0-50% material with carbon element, ultrasonic disperse obtains the aqueous solution of polymer monomer, and this process is under nitrogen or argon gas atmosphere are protected
Carry out；
B: oxidant and adulterant Iron(III) chloride hexahydrate are dissolved in deionized water, then by Iron(III) chloride hexahydrate water
Solution is added dropwise in the aqueous solution of above-mentioned polymer monomer, and the mol ratio wherein controlling ferric chloride and polymer monomer is 2-4:
1；React 3-10 hour under conditions of keeping ultrasonic, atmosphere protection；Then through taking out chlorine, cleaning and be vacuum dried, chlorine doping is obtained
Polymer matrix composite.
The polymer matrix composite of chlorine of the present invention doping can significantly improve chloride ion cell positive material
Cyclical stability, has important impetus to development high stable chloride ion battery.
At two electrode systems, (or three battery systems, containing reference in the electrode performance test of the positive electrode obtained by the present invention
Electrode) under the conditions of carry out, negative pole is lithium electrode, and reference electrode is platinum electrode, and electrolyte is the hybrid ionic that can conduct chloride ion
Liquid.
Beneficial effect:
The polymer matrix composite of chlorine provided by the present invention doping can solve chloride ion battery metal chloride positive pole
The precipitation problem of material and the metal oxychloride positive electrode bigger change in volume problem in charge and discharge process, it is possible to
Significantly improve the cyclical stability of chloride ion cell positive material, development high stable chloride ion battery is had important promotion and makees
With.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the composite of chlorination polypyrrole and the CNT prepared in embodiment 1；
Fig. 2 is the energy spectrogram of the composite of chlorination polypyrrole and the CNT prepared in embodiment 1；
Fig. 3 is the charging and discharging curve figure of positive electrode and lithium titanate cathode material in embodiment 1；
Fig. 4 is positive electrode and the cyclic voltammogram of lithium titanate cathode material in embodiment 1.
Detailed description of the invention
The polymer matrix composite of example below chlorine doping all uses chemical reduction method to prepare, and specifically comprises the following steps that
A: polymer monomer pyrroles, aniline or the thiophene through distillation purifying is scattered in the deionized water through ice bath cooling
In, adding 0-50% material with carbon element, ultrasonic disperse obtains the aqueous solution of polymer monomer, and this process is under nitrogen or argon gas atmosphere are protected
Carry out；
B: be dissolved in deionized water by Iron(III) chloride hexahydrate, is then added dropwise to above-mentioned by Iron(III) chloride hexahydrate aqueous solution
In the aqueous solution of polymer monomer, the mol ratio wherein controlling ferric chloride and polymer monomer is 2-4:1；Keep ultrasonic, gas
React 3-10 hour under conditions of atmosphere protection；Then through taking out chlorine, cleaning and be vacuum dried, the polymer base composite wood of chlorine doping is obtained
Material.
Embodiment 1:
1), material preparation and battery assemble: with pyrroles (0.42ml) as monomer, CNT is carbon base body, deionized water
For reaction medium, Iron(III) chloride hexahydrate (50ml, 0.29M) is oxidant and chlorine dopant, Iron(III) chloride hexahydrate and pyrroles
The mol ratio of monomer is 2.35:1；Wherein CNT uses sulphuric acid/nitric acid to carry out oxidation processes.(anti-by chemical reduction method
Answer 4 hours) prepare chlorination polypyrrole based composites (content of carbon nanotubes is 18%), this process is entered under nitrogen atmosphere is protected
OK；Pattern is as shown in Figure 1；Power spectrum result in Fig. 2 indicates the Effective Doping of chlorine element in polymer composites.This is multiple
Condensation material is coated onto on stainless (steel) wire after acetylene black, PTFE mixing, then colds pressing and makes anode electrode；Negative material is Li, electricity
Solving liquid is 0.5M PP14Cl/PP14TFSI mixed ionic liquid.
2), charge-discharge test result show (as shown in Figure 3), polypyrrole positive electrode discharge capacity first is 93mAh/g.
After activation first, battery discharge platform significantly improves, and shows preferable cyclical stability.
3), cyclic voltammetric result show (as shown in Figure 4), there is bigger activation polarization in polypyrrole first charge-discharge；
After activated, at 2.4 and 2.8V, occur in that significantly reduction and oxidation peak respectively.After circulation, the oxidoreduction of electrode is anti-
Should tend towards stability, consistent with discharge and recharge result.
Embodiment 2:
1), material prepares and battery assembles: with pyrroles (0.42ml) as monomer, Iron(III) chloride hexahydrate (50ml, 0.49M)
For oxidant and chlorine dopant, deionized water be the mol ratio of reaction medium, Iron(III) chloride hexahydrate and pyrrole monomer be 4:1,
Preparing chlorination polypyrrole by chemical reduction method (reacting 10 hours), this process is carried out under argon gas atmosphere is protected；C, N, H element
Analysis shows, the C:N:H of obtained polypyrrole is 3.98:1:3.04, forms very close to theory.By polypyrrole and acetylene black,
It is coated onto on stainless (steel) wire after PTFE mixing, then colds pressing and make anode electrode；Negative material is Li, and electrolyte is 0.5M
PP14Cl/PP14TFSI mixed ionic liquid.
2), charge-discharge test result show, polypyrrole positive electrode discharge capacity first is 105mAh/g.Through 30 circulations
After, discharge capacity is about 80mAh/g.Visible, use polypyrrole material prepared by same procedure, carbon nanotubes matrix is impure
The capacity of polypyrrole is less than Pt/Polypyrrole composite material containing nanotube matrix, and it is poly-that this is likely due to deposit on the carbon nanotubes
Azole materials has the nanostructured of excellence, improves electronics and the ionic conduction ability of electrode material, thus improves its electricity
Chemical property.
Embodiment 3:
1), material preparation and battery assemble: with thiophene (0.4ml) as monomer, CNT is carbon base body, six hydration trichlorines
Changing ferrum (50ml, 0.3M) is oxidant and chlorine dopant, and deionized water is reaction medium, Iron(III) chloride hexahydrate and pyrrole monomer
Mol ratio be 3:1；Wherein CNT uses sulphuric acid/nitric acid to carry out oxidation processes.By chemical reduction method (reacting 6 hours)
Preparing chlorination polythiophene based composites (content of carbon nanotubes is 35%), this process is carried out under nitrogen atmosphere is protected；Should
Composite is coated onto on stainless (steel) wire after acetylene black, PTFE mixing, then colds pressing and makes anode electrode；Negative material is Li,
Electrolyte is 0.5M PP14Cl/PP14TFSI mixed ionic liquid.
2), charge-discharge test result show, polythiophene positive electrode discharge capacity first is 85mAh/g.Activate through first
After, battery discharge platform significantly improves, and shows preferable cyclical stability.
Embodiment 4:
1), material preparation and battery assemble: with aniline (0.4ml) as monomer, Graphene is carbon base body, six trichloride hydrate
Ferrum (50ml, 0.2M) is oxidant and chlorine dopant, and deionized water is reaction medium, Iron(III) chloride hexahydrate and pyrrole monomer
Mol ratio is 2:1；；Wherein Graphene uses sulphuric acid/nitric acid to carry out oxidation processes.By chemical reduction method, (response time 3 is little
Time) preparing chlorinated polyphenyl amido composite (Graphene content is 50%), this process is carried out under argon gas atmosphere is protected；Should
Composite is coated onto on stainless (steel) wire after acetylene black, PTFE mixing, then colds pressing and makes anode electrode；Negative material is Li,
Electrolyte is 0.5M PP14Cl/PP14TFSI mixed ionic liquid.
2), charge-discharge test result show, polyaniline positive electrode discharge capacity first is 65mAh/g.Activate through first
After, battery discharge platform significantly improves, and shows preferable cyclical stability.
A kind of polymer matrix composite through chlorine doping prepared according to design philosophy and the design of the present invention, its
The content of the poly-inclusion of middle chlorine doping is 50-100%, and the content of material with carbon element is 0-50%.The exploitation of this novel anode material can
The precipitation problem of solution chloride ion battery metal chloride positive electrode and metal oxychloride positive electrode are in discharge and recharge
Bigger change in volume problem in journey, it is possible to significantly improve the cyclical stability of chloride ion cell positive material, to development height
Stablize chloride ion battery and there is important impetus.
Claims (5)
1. the polymer matrix composite of chlorine doping application in chloride ion cell positive material.
Application the most according to claim 1, it is characterised in that in the polymer matrix composite of described chlorine doping, chlorine is mixed
The quality of miscellaneous polymer accounts for the 50-100% of polymer matrix composite quality, and the quality of material with carbon element accounts for polymer base composite wood
The 0-50% of material quality.
Application the most according to claim 1, it is characterised in that the polymer of described chlorine doping is chlorination polypyrrole, chlorination
Polyaniline or chlorination polythiophene.
Application the most according to claim 1, it is characterised in that described material with carbon element is CNT, Graphene, carbon black, carbon
Fiber or porous carbon.
Application the most according to claim 1, it is characterised in that the polymer matrix composite employingization of described chlorine doping
Prepared by reducing process, specifically comprise the following steps that
A: polymer monomer pyrroles, aniline or the thiophene through distillation purifying is scattered in the deionized water of ice bath cooling, adds
Entering 0-50% material with carbon element, ultrasonic disperse obtains the aqueous solution of polymer monomer, and this process is carried out under nitrogen or argon gas atmosphere are protected；
B: be dissolved in deionized water by Iron(III) chloride hexahydrate, is then added dropwise to above-mentioned polymerization by Iron(III) chloride hexahydrate aqueous solution
In the aqueous solution of thing monomer, the mol ratio wherein controlling ferric chloride and polymer monomer is 2-4:1；Keep ultrasonic, atmosphere guarantor
React 3-10 hour under conditions of protecting；Then through taking out chlorine, cleaning and be vacuum dried, the polymer matrix composite of chlorine doping is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610812191.0A CN106299288B (en) | 2016-09-08 | 2016-09-08 | A kind of application of the polymer matrix composite of chlorine doping in chloride ion cell positive material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610812191.0A CN106299288B (en) | 2016-09-08 | 2016-09-08 | A kind of application of the polymer matrix composite of chlorine doping in chloride ion cell positive material |
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| Publication Number | Publication Date |
|---|---|
| CN106299288A true CN106299288A (en) | 2017-01-04 |
| CN106299288B CN106299288B (en) | 2019-03-01 |
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Cited By (3)
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| CN109546209A (en) * | 2018-11-07 | 2019-03-29 | 南京工业大学 | A kind of full solid state polymer electrolyte and chargeable chloride ion battery |
| CN113078312A (en) * | 2021-03-26 | 2021-07-06 | 南京工业大学 | Bismuth chloride @ porous carbon composite chloride ion battery positive electrode material and preparation method thereof |
| CN116063674A (en) * | 2021-11-01 | 2023-05-05 | 华北电力大学（保定） | Aimed at gaseous Hg O Preparation method of chlorine doped protonated polypyrrole adsorbent |
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| US20140234753A1 (en) * | 2010-09-28 | 2014-08-21 | Battelle Memorial Institute | Redox flow batteries based on supporting solutions containing chloride |
| CN104241711A (en) * | 2014-05-16 | 2014-12-24 | 南京工业大学 | Chloride ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109546209A (en) * | 2018-11-07 | 2019-03-29 | 南京工业大学 | A kind of full solid state polymer electrolyte and chargeable chloride ion battery |
| CN109546209B (en) * | 2018-11-07 | 2021-10-29 | 南京工业大学 | All-solid-state polymer electrolyte and rechargeable chloride ion battery |
| CN113078312A (en) * | 2021-03-26 | 2021-07-06 | 南京工业大学 | Bismuth chloride @ porous carbon composite chloride ion battery positive electrode material and preparation method thereof |
| CN116063674A (en) * | 2021-11-01 | 2023-05-05 | 华北电力大学（保定） | Aimed at gaseous Hg O Preparation method of chlorine doped protonated polypyrrole adsorbent |
| CN116063674B (en) * | 2021-11-01 | 2023-09-29 | 华北电力大学（保定） | Aimed at gaseous Hg O Preparation method of chlorine doped protonated polypyrrole adsorbent |
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| CN106299288B (en) | 2019-03-01 |
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