CN117219748A - Negative electrode material, negative electrode plate and potassium ion battery with negative electrode plate - Google Patents
Negative electrode material, negative electrode plate and potassium ion battery with negative electrode plate Download PDFInfo
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- CN117219748A CN117219748A CN202311292555.3A CN202311292555A CN117219748A CN 117219748 A CN117219748 A CN 117219748A CN 202311292555 A CN202311292555 A CN 202311292555A CN 117219748 A CN117219748 A CN 117219748A
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- negative electrode
- ion battery
- mxene
- solution
- potassium ion
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- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 41
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 36
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 36
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 36
- 235000020232 peanut Nutrition 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 34
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 33
- NGSHGXOAGJWPLZ-UHFFFAOYSA-L [K+].[K+].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 Chemical compound [K+].[K+].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 NGSHGXOAGJWPLZ-UHFFFAOYSA-L 0.000 claims abstract description 22
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001088 polycarbazole Polymers 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- WCBFEMZIZMFMPB-UHFFFAOYSA-L dipotassium;naphthalene-1,2-dicarboxylate Chemical compound [K+].[K+].C1=CC=CC2=C(C([O-])=O)C(C(=O)[O-])=CC=C21 WCBFEMZIZMFMPB-UHFFFAOYSA-L 0.000 claims abstract description 8
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 claims abstract description 7
- 241001553178 Arachis glabrata Species 0.000 claims abstract 10
- 239000000243 solution Substances 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 229960003351 prussian blue Drugs 0.000 claims description 16
- 239000013225 prussian blue Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- APSDTEHUYIJMPZ-UHFFFAOYSA-N 9h-carbazole;hydrochloride Chemical compound Cl.C1=CC=C2C3=CC=CC=C3NC2=C1 APSDTEHUYIJMPZ-UHFFFAOYSA-N 0.000 claims description 7
- YDTNJZGJJUBGTD-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid;potassium Chemical compound [K].[K].C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 YDTNJZGJJUBGTD-UHFFFAOYSA-N 0.000 claims description 7
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- LFDGRWDETVOGDT-UHFFFAOYSA-N 1h-pyrrole;hydrochloride Chemical compound Cl.C=1C=CNC=1 LFDGRWDETVOGDT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 239000012154 double-distilled water Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229940037179 potassium ion Drugs 0.000 claims 11
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 244000105624 Arachis hypogaea Species 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- VRWKTAYJTKRVCU-UHFFFAOYSA-N iron(6+);hexacyanide Polymers [Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] VRWKTAYJTKRVCU-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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 invention relates to a negative electrode material, a negative electrode plate and a potassium ion battery with the negative electrode plate, wherein the negative electrode material provided by the invention is prepared by compounding MXene material with peanut shell biochar, so that the easy stacking phenomenon of the MXene material is improved, and the obtained MXene/peanut shell biochar composite material is combined with dipotassium naphthalene dicarboxylate through chemical bonds to form a stable and efficient conductive composite material. And then, the dipotassium naphthalate@MXene/peanut shell biochar composite material is used as a negative electrode material, the polycarbazole/polypyrrole modified Prussian blue material is used as a positive electrode material to prepare a positive electrode plate and a negative electrode plate, and the positive electrode plate, the negative electrode plate and a potassium triflate aqueous solution are used as electrolyte to assemble a water-based potassium ion battery, wherein the capacity retention rate of the water-based potassium ion battery after 1000 cycles is more than 85%, the water-based potassium ion battery has excellent conductivity and rate capability, and a theoretical basis is provided for promoting the large-scale application of the water-based alkali metal battery.
Description
Technical Field
The invention belongs to the technical field of energy storage and power batteries, and particularly relates to a negative electrode material, a negative electrode plate and a potassium ion battery with the negative electrode plate.
Background
Lithium ion batteries are one of the most widely used rechargeable batteries at present, but their further development is limited due to the rarity and safety problems of lithium resources and recycling environmental protection problems. The water system alkali metal ion battery has the advantages of high safety, low price, environmental friendliness and the like, and has wide application prospect in the technical field of large-scale energy storage. Among the aqueous alkali metal ion batteries, aqueous potassium ion batteries are the best candidate materials for replacing lithium ion batteries due to the advantages of low cost, high energy density, high ion conductivity, safety and environmental protection.
MXene is used as a novel two-dimensional material, has a graphene-like layered structure, and has the advantages of higher specific surface area, conductivity, excellent hydrophilicity, and abundant surface tube energy groups and active sites. The method has wide application prospect in the technical fields of energy storage, power batteries and the like, however, the MXene material is easy to generate stacking phenomenon, so that a great amount of active sites are lost, the theoretical specific capacity is low, and the application effect is not easy to develop;
in addition, because a plurality of electrode materials are dissolved in the aqueous electrolyte and generate more byproducts, the structure and electrochemical stability of the materials are affected, and the electrochemical stability window of the traditional aqueous electrolyte is narrow, the selection of the electrode materials in the aqueous battery is greatly limited, so that the electrode materials suitable for the aqueous potassium ion battery are found out, and the large-scale application of the aqueous alkali metal battery can be greatly promoted.
Disclosure of Invention
The invention aims to solve the problems and provide a negative electrode material, a negative electrode sheet and a potassium ion battery with the negative electrode sheet.
The invention realizes the above purpose through the following technical scheme:
in a first aspect, the invention provides a negative electrode material, which is a dipotassium naphthalate@MXene/peanut shell biochar composite material obtained by modifying dipotassium naphthalate with an MXene/peanut shell biochar composite material.
In a second aspect, the present invention further provides a negative electrode sheet containing the negative electrode material described above.
In a third aspect, the present invention further provides a method for preparing a negative electrode material, comprising the steps of,
(1) Slowly adding potassium hydroxide aqueous solution into naphthalene dicarboxylic acid until naphthalene dicarboxylic acid solid is completely dissolved, adding into double distilled water with peroxide removed, stirring to obtain naphthalene dicarboxylic acid dipotassium aqueous solution, and finally drying and dehydrating naphthalene dicarboxylic acid dipotassium aqueous solution to obtain naphthalene dicarboxylic acid dipotassium crystal;
(2) Preparing an MXene/biochar composite material, weighing MXene powder and peanut shell biochar, adding the MXene powder and the peanut shell biochar into deionized water, stirring, washing the stirred solution with deionized water, carrying out suction filtration, and carrying out vacuum drying to obtain the MXene/peanut shell biochar composite material;
(3) Preparing a dipotassium naphthalate@MXene/peanut shell biochar composite material, dispersing the MXene/biochar composite material in dimethylformamide, adding dipotassium naphthalate crystals after ultrasonic treatment, stirring until the mixture is clear, then adding Dbu (1, 8-diazabicyclo undec-7-ene) and stirring to obtain a mixed solution, alternately centrifuging the mixed solution with ethanol and deionized water, drying a solid matter, and carrying out heat treatment and cooling on an obtained product to obtain the dipotassium naphthalate@MXene/peanut shell biochar composite material.
In the step (3), the heat treatment is specifically performed in an argon atmosphere at a temperature of 300 ℃ for 1h, at a temperature of 500 ℃ at 5 ℃/min for 2h.
In a fourth aspect, the invention further provides an aqueous potassium ion battery, which comprises a positive plate, electrolyte and the negative plate.
As a further optimization scheme of the invention, the positive plate comprises a positive electrode material, and the positive electrode material is a polycarbazole/polypyrrole modified Prussian blue material.
As a further optimization scheme of the invention, the preparation method of the polycarbazole/polypyrrole modified Prussian blue material comprises the following steps of,
(1) Preparation of Prussian blue Material KCl and K 4 Fe(CN) 6 ·10H 2 O is added into a reactor containing deionized water to form solution A, feCl is added into the solution A 2 ·4H 2 Adding 0 and potassium citrate into deionized water to form a complexing solution B, dripping the solution B into the solution A in nitrogen atmosphere, simultaneously independently dripping a potassium hydroxide solution and ammonia water into a reactor to react, stirring vigorously while dripping, standing the suspension after the reaction is finished to obtain a precipitate, centrifuging and washing the precipitate by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the Prussian blue material;
(2) And (3) preparing the polycarbazole/polypyrrole modified Prussian blue material, dispersing the Prussian blue material in deionized water to form a suspension A, adding a carbazole hydrochloride solution or a carbazole hydrochloride solution into the suspension A, continuously stirring, taking a precipitate, centrifuging and washing the precipitate by using deionized water and absolute ethyl alcohol, and vacuum drying to obtain the polycarbazole/polypyrrole modified Prussian blue material.
As a further optimization scheme of the invention, the potassium ion battery is a solid, semi-solid or water-based potassium ion battery.
As a further optimization scheme of the invention, when the potassium ion battery is an aqueous potassium ion battery, the electrolyte is a potassium trifluoromethane sulfonate aqueous solution.
As a further optimization scheme of the invention, when the potassium ion battery is a solid-state battery, the electrolyte is one of polyacrylic imide, polyvinyl alcohol or polyethylene oxide.
The invention has the beneficial effects that:
(1) The composite material of the peanut shell biochar provided by the invention is prepared by compounding the peanut shell biochar with the MXene material, the phenomenon that the MXene material is easy to stack is improved, and the obtained MXene/peanut shell biochar composite material is combined with dipotassium naphthalene dicarboxylate through chemical bonds to form a stable and efficient conductive composite material.
(2) According to the invention, the dipotassium naphthalate@MXene/peanut shell biochar composite material is used as a negative electrode material, the polycarbazole/polypyrrole modified Prussian blue material is used as a positive electrode material, and the aqueous potassium triflate aqueous solution is used as an electrolyte to assemble the aqueous potassium ion battery, wherein the capacity retention rate of the aqueous potassium ion battery is above 85% after 1000 circles are circulated, the aqueous potassium ion battery has excellent conductivity and multiplying power performance, and a theoretical basis is provided for promoting the large-scale application of the aqueous alkali metal battery.
Drawings
Fig. 1 is an infrared spectrogram of the positive electrode material provided by the invention.
Fig. 2 is an electrochemical window diagram of the aqueous potassium ion battery provided by the invention.
Fig. 3 is a cycle performance chart of the aqueous potassium ion battery provided by the invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, wherein it is to be understood that the following detailed description is for the purpose of further illustrating the invention only and is not to be construed as limiting the scope of the invention, as various insubstantial modifications and adaptations of the invention to those skilled in the art can be made in light of the foregoing disclosure.
1. Materials and methods
The methods are conventional unless otherwise indicated, and the materials are commercially available from the public sources unless otherwise indicated.
1. Preparation of negative electrode material
1.1 preparation of dipotassium naphthalene dicarboxylate
(1) Taking 100ml of double distilled water in a blue glass cover bottle, continuously introducing nitrogen for 30 minutes, removing oxygen in the water, and adding a magnetic stirring rotor for standby;
(2) Weighing 0.56g of potassium hydroxide, adding the potassium hydroxide into a blue glass cover bottle, and stirring to prepare 0.1mol of potassium hydroxide aqueous solution;
(3) 2.16g of naphthalene dicarboxylic acid is weighed and added into a blue glass cover bottle, then 0.1mol of potassium hydroxide aqueous solution is slowly added until the naphthalene dicarboxylic acid solid is completely disappeared, and a magnetic stirring rotor is added for stirring for 30min, so as to obtain a clear and transparent solution, namely the dipotassium naphthalene dicarboxylic acid aqueous solution. Transferring the dipotassium naphthalate aqueous solution into a blast drying box at 100 ℃, and gradually removing water in the solution to obtain high-purity dipotassium naphthalate crystals.
1.2 preparation of MXene/peanut shell biochar composite Material
(1) Preparing peanut shell biochar, namely putting the peanut shell into a pulverizer to pulverize into powder, and then drying the powder in a blast drying oven at 100 ℃ for 12 hours. And (3) loading the dried peanut shell powder into a crucible, putting the crucible into a tube furnace, heating to 500 ℃ at a heating speed of 10 ℃/min under a nitrogen atmosphere, and staying for 2 hours. Cooling to about 55deg.C, taking out to obtain peanut shell charcoal, cleaning ash on the surface for 1-2 times, oven drying, grinding, and sieving with 60 mesh sieve;
grinding potassium hydroxide and peanut shell carbon (peanut shell carbon weight is 2 g) in a mortar according to a mass ratio of 4:1, drying in a drying oven, then performing high-temperature activation in a tube furnace, heating from room temperature to 300 ℃ at a heating speed of 5 ℃/min under a nitrogen environment, staying for 1h, heating to 750 ℃ at a heating speed of 5 ℃/min, preserving heat for 4h, taking out the material after the furnace is cooled to about 55 ℃, and then cleaning with deionized water. The solution was washed with 0.1mol/L dilute hydrochloric acid until neutral. Washing the solution with deionized water, filtering, and drying in a vacuum drying oven at 120deg.C for 12 hr;
(2) Preparation of MXene Material 80ml of 9M hydrochloric acid solution were added to a Teflon beaker, 4.0g LiF was added, and mechanical stirring was carried out for 30min until LiF was completely dissolved, ti was dissolved 3 AlC 2 The powder was slowly added to the solution and stirred using a constant temperature magnetic stirrer for 24h at 30 ℃. The resulting product was then transferred to a centrifuge tube and centrifuged at 4500rpm for 5min, and repeated centrifugation with deionized water until the suspension pH was neutral. The centrifuge tube was sonicated in an ice water bath for 1h, after sonication, centrifuged at 4500rpm for 5min, and the supernatant was collected. Finally, the centrifuge tube is placed into a vacuum drying box for vacuum drying for 48 hours, and MXene powder is obtained for standby.
1.3 preparation of MXene/peanut shell biochar composite Material
2g of MXene powder and 4g of peanut shell biochar were weighed, 400ml of deionized water was added, and stirred using a constant temperature magnetic stirrer at 25℃for 6 hours. Washing the stirred solution with deionized water for 2-3 times, filtering, vacuum drying in a vacuum drying oven at 120 ℃ for 12 hours, and finally obtaining the MXene/peanut shell biochar composite material.
1.4 preparation of dipotassium naphthalate @ MXene/peanut shell biochar composite material
100mg of MXene/peanut shell charcoal composite material was dispersed in 25mL of Dimethylformamide (DMF) and sonicated for 20h to ensure complete exfoliation. Then adding 11.455g of dipotassium naphthalate, stirring until the dipotassium naphthalate is clear, adding 5ml of Dbu, stirring for 12 hours, alternately centrifuging the mixed solution with ethanol and deionized water for 3-4 times, pouring out supernatant, putting the solid in a centrifuge tube into a blast drier for drying, putting the obtained product into a tube furnace, heating to 300 ℃ within 1 hour under argon, preserving heat for 1 hour, heating to 500 ℃ at 5 ℃/min, preserving heat for 2 hours, cooling to 55 ℃ in the furnace, and taking out the material, thus obtaining the dipotassium naphthalate@MXene/peanut shell biochar composite material.
2. Preparation of cathode Material
2.1 preparation of Prussian blue Material
(1) 10g of KCl and 0.002mol of K are weighed 4 Fe(CN) 6 ·10H 2 O is added into a reactor containing 100mL of deionized water to form solution A;
(2) 0.004mol FeCl 2 ·4H 2 O and 0.008mol potassium citrate are added into 100mL deionized water to form a complexing solution B;
(3) Solution B was dropped into solution A by a peristaltic pump at a rate of 1mL/min under a nitrogen atmosphere, and simultaneously, 5M potassium hydroxide solution and 1.7M aqueous ammonia were independently added to the reactor in a drop of 1.2mL/min to carry out the reaction, and the reaction temperature was 55℃with vigorous stirring, and after 6 hours the reaction was allowed to stand for 24 hours. And centrifuging and washing the precipitate for 3-4 times by using deionized water and absolute ethyl alcohol, and finally drying the product in a vacuum oven at 120 ℃ for 12 hours to obtain the Prussian blue material.
2.2 preparation of Prussian blue materials modified by polycarbazole/polypyrrole
(1) Preparing a 0.1M carbazole hydrochloride solution: 1.156g of carbazole hydrochloride is dissolved in 95.8mL of deionized water, and 4.2mL of concentrated hydrochloric acid is added to prepare 100mL of carbazole hydrochloride solution for later use;
(2) Preparing a 0.1M pyrrole hydrochloride solution: dissolving 0.986g of aniline hydrochloride in 95.8mL of deionized water, and adding 4.2mL of concentrated hydrochloric acid to prepare 100mL of pyrrole hydrochloride solution for later use;
(3) Then, 0.5g of the Prussian blue material prepared above was ultrasonically dispersed in 100mL of deionized water for 30 minutes to form suspension A. Adding the prepared carbazole hydrochloride solution or pyrrole hydrochloride solution into the suspension A, continuously stirring for 24 hours, and centrifuging and washing the precipitate for 3-4 times by using deionized water and absolute ethyl alcohol. Finally, drying the product in a vacuum oven at 120 ℃ for 12 hours to obtain the polycarbazole/polypyrrole modified Prussian blue material.
3. Preparation of aqueous potassium ion battery
(1) The positive and negative electrode materials, the binder and the conductive agent are prepared into positive and negative electrode sheets, wherein the binder comprises carboxymethyl cellulose, polyacrylonitrile, polyvinyl alcohol, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene acrylic ester and the like, the dosage is between 2 and 5 percent of the mass of the positive and negative electrode materials, and the conductive agent comprises graphite, carbon black, acetylene black, carbon nanotubes, conductive polymer and the like, and the dosage is between 5 and 15 percent of the mass of the positive and negative electrode materials.
(2) Sequentially stacking the positive electrode shell, the positive electrode plate, the PP diaphragm, the negative electrode plate, the gasket, the elastic sheet and the negative electrode shell together, wherein after the diaphragm is placed, electrolyte (22 mol/L potassium trifluoromethane sulfonate aqueous solution) is dropwise added to the PP diaphragm, the electrolyte is dropwise added to the diaphragm to infiltrate the positive electrode plate and the PP diaphragm, and then the negative electrode plate is placed; then, the aqueous potassium ion 2032 type button cell was assembled by a hydraulic button cell packaging machine.
2. Verification test
1. To verify the performance impact of the anode material on aqueous potassium ion batteries, the following groupings were used as the anode material:
a first group: dipotassium naphthalene dicarboxylate;
second group: dipotassium naphthalate@MXene composite material;
third group: dipotassium naphthalate@MXene/peanut shell biochar composite material;
fourth group: dipotassium naphthalate@MXene/corn stalk biochar composite material;
fifth group: dipotassium naphthalate@MXene/walnut shell biochar composite material;
sixth group: dipotassium naphthalate@MXene/wood charcoal composite material;
the positive electrode plate and the negative electrode plate are prepared from the composite materials of the groups, the prussian blue material modified by the polycarbazole and prepared in the step 2.2, 2 percent of carboxymethyl cellulose and 10 percent of graphite, and the aqueous potassium ion 2032 button battery is assembled by taking 22mol/L of potassium triflate aqueous solution as electrolyte according to the preparation method in the step 3. Electrochemical performance was tested on the cell samples. Including the initial charge specific capacity at 0.1C and 1C and the initial discharge specific capacity at 1C, the capacity retention rate and the rate capability (i.e., the normal temperature 4C discharge specific capacity, specifically, the normal temperature 0.1C to 2.5V,0.1C to 0V, 0.5C to 2.5V,0.5C to 0V,1C to 2.5V,1C to 0V,4C to 2.5V,4C to 0V) were cycled at 1C and at 45℃, and the test results are shown in table 1.
TABLE 1 electrochemical Performance test results Table for cell samples 1-8
As can be seen from table 1, the electrochemical performance data of comparative samples 1-3 show that the electrochemical performance data of samples 1-3 are not favorable for improving the conductivity of the battery, and presumably because the molecular structure of the dipotassium naphthalate contains a large number of single carbon-carbon bonds and carbon-oxygen bonds, the covalent characteristics of the bonds prevent the electron transmission in the molecule, so that the conductivity of the dipotassium naphthalate is limited, sample 2 modifies the dipotassium naphthalate by using the MXene material, the MXene has a graphene-like layered structure, has higher specific surface area and conductivity, excellent hydrophilicity and rich surface functional groups and active sites, and further the conductivity of sample 2 is improved compared with sample 1, but sample 2 is not as high as sample 3-6, and presumably because the MXene material is easy to generate a stacking phenomenon, the active sites are greatly lost, the theoretical specific capacity is lower, the sample 3-6 adopts different biochar materials to be compounded with the MXene material, the stacking phenomenon of the MXene material can be significantly improved, and the electrochemical performance data of samples 3-6 can show that the biochar shell has the best effect.
2. To verify the effect of the positive electrode material on the performance of the aqueous potassium ion battery, the following groups were used as the positive electrode materials,
a: polycarbazole-modified Prussian blue materials;
b: polypyrrole modified Prussian blue materials;
CK: unmodified normal Prussian blue material;
the three materials were each subjected to infrared spectroscopic analysis, the results of which are shown in FIG. 1. As can be seen from FIG. 1, all three samples were at 2100cm -1 A significant characteristic peak appears at the left and right, which is the telescopic vibration absorption peak of cyano-c≡n in prussian blue material. While at 600cm -1 The characteristic peak of the modified polycarbazole/polypyrrole material is weaker than the peak of the modified polycarbazole/polypyrrole material under the wavelength, and the modification can weaken the stretching vibration of the Fe-CN group. 1600cm -1 The characteristic peak at this point is-c=c-the telescopic vibration absorption peak. Cm around 3000 -1 The broad peak between the modified material and the modified material is N-H stretching vibration absorption peak, and compared with the common Prussian blue material, the modified material has characteristic absorption peaks of polycarbazole and polypyrrole, which indicates that the conductive polymer polycarbazole and polypyrrole are successfully combined with the Prussian blue material.
In addition, the dipotassium naphthalene dicarboxylate@MXene/peanut shell biochar composite material prepared in the step 1.4 is used as a negative electrode material, the negative electrode material and 2% of carboxymethyl cellulose and 10% of graphite are respectively prepared to obtain a positive electrode sheet and a negative electrode sheet, a 22mol/L potassium triflate aqueous solution is used as an electrolyte, an aqueous potassium ion 2032 type button cell sample is assembled according to the preparation method in the step 3, and the electrochemical window of the cell sample and the cycle performance of the cell are tested, wherein the results are shown in fig. 2-3.
As can be seen from fig. 2, the positive electrode material for a is a polycarbazole-modified prussian blue material, and the positive electrode material for B is a polypyrrole-modified prussian blue material. A has a wide electrochemical window of 3.45V, with a negative window of-1.85V and a positive window of 1.60V. B has a wide electrochemical window of 3.08V, with a negative window of-1.45V and a positive window of 1.63V. The aqueous potassium ion battery modified by the conductive polymer has a wider electrochemical window.
As can be seen from fig. 3, the positive electrode material for a is a polycarbazole-modified prussian blue material, and the positive electrode material for B is a polypyrrole-modified prussian blue material. The capacity retention rate of the potassium ion water-based battery prepared by the two positive electrode materials is above 80% after 1000 circles, wherein the capacity retention rate of the prussian blue material modified by the polycarbazole after 1000 circles is 85%. The aqueous potassium ion battery manufactured by using the anode and the cathode has excellent electrochemical performance.
While the foregoing description illustrates and describes several preferred embodiments of the invention, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of use in various other combinations, modifications and environments and is capable of changes or modifications within the spirit of the invention described herein, either as a result of the foregoing teachings or as a result of the knowledge or skill of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (10)
1. The negative electrode material is characterized in that the negative electrode material is a dipotassium naphthalate@MXene/peanut shell biochar composite material obtained by modifying dipotassium naphthalate with an MXene/peanut shell biochar composite material.
2. A negative electrode sheet containing the negative electrode material according to claim 1.
3. A method for producing a negative electrode material according to claim 1, comprising the steps of,
(1) Slowly adding potassium hydroxide aqueous solution into naphthalene dicarboxylic acid until naphthalene dicarboxylic acid solid is completely dissolved, adding into double distilled water with peroxide removed, stirring to obtain naphthalene dicarboxylic acid dipotassium aqueous solution, and finally drying and dehydrating naphthalene dicarboxylic acid dipotassium aqueous solution to obtain naphthalene dicarboxylic acid dipotassium crystal;
(2) Preparing an MXene/biochar composite material, weighing MXene powder and peanut shell biochar, adding the MXene powder and the peanut shell biochar into deionized water, stirring, washing the stirred solution with deionized water, carrying out suction filtration, and carrying out vacuum drying to obtain the MXene/peanut shell biochar composite material;
(3) Preparing a dipotassium naphthalene dicarboxylate@MXene/peanut shell biochar composite material, dispersing the MXene/biochar composite material in dimethylformamide, adding dipotassium naphthalene dicarboxylate after ultrasonic treatment, stirring until the mixture is clear, adding Dbu, stirring to obtain a mixed solution, alternately centrifuging the mixed solution with ethanol and deionized water, keeping solids, drying, and carrying out heat treatment and cooling on the obtained product to obtain the dipotassium naphthalene dicarboxylate@MXene/peanut shell biochar composite material.
4. The method according to claim 3, wherein in the step (3), the heat treatment is specifically performed in an argon atmosphere at a temperature of 300 ℃ for 1 hour, at a temperature of 5 ℃/min to 500 ℃, and at a temperature of 2 hours.
5. A potassium ion battery comprising a positive electrode sheet, an electrolyte, and the negative electrode sheet of claim 2.
6. The potassium ion battery of claim 5, wherein the positive electrode sheet comprises a positive electrode material, and the positive electrode material is a polycarbazole/polypyrrole modified Prussian blue type material.
7. The potassium ion battery of claim 6, wherein the preparation method of the polycarbazole/polypyrrole modified Prussian blue material comprises the following steps of,
(1) Preparation of Prussian blue Material KCl and K 4 Fe(CN) 6 ·10H 2 O is added into a reactor containing deionized water to form solution A, feCl is added into the solution A 2 ·4H 2 Adding 0 and potassium citrate into deionized water to form a complexing solution B, dripping the solution B into the solution A in nitrogen atmosphere, simultaneously independently dripping a potassium hydroxide solution and ammonia water into a reactor to react, stirring vigorously while dripping, standing the suspension after the reaction is finished to obtain a precipitate, centrifuging and washing the precipitate by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the Prussian blue material;
(2) And (3) preparing the polycarbazole/polypyrrole modified Prussian blue material, dispersing the Prussian blue material in deionized water to form a suspension A, adding a carbazole hydrochloride solution or a pyrrole hydrochloride solution into the suspension A, continuously stirring, taking a precipitate, centrifuging and washing the precipitate by using deionized water and absolute ethyl alcohol, and vacuum drying to obtain the polycarbazole/polypyrrole modified Prussian blue material.
8. The potassium-ion battery of claim 5, wherein the potassium-ion battery is a solid, semi-solid, or aqueous potassium-ion battery.
9. The potassium ion battery of claim 8, wherein when the potassium ion battery is an aqueous potassium ion battery, the electrolyte is an aqueous solution of potassium triflate.
10. The potassium ion battery of claim 8, wherein when the potassium ion battery is a solid state battery, the electrolyte is one of a polyacrylic imide, a polyvinyl alcohol, or a polyethylene oxide.
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