CN113161603A - Novel potassium ion battery and preparation method thereof - Google Patents
Novel potassium ion battery and preparation method thereof Download PDFInfo
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- CN113161603A CN113161603A CN202110373512.2A CN202110373512A CN113161603A CN 113161603 A CN113161603 A CN 113161603A CN 202110373512 A CN202110373512 A CN 202110373512A CN 113161603 A CN113161603 A CN 113161603A
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- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 83
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 41
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- ZRIKJQADWGOGIW-UHFFFAOYSA-N [K][Mn][Fe] Chemical compound [K][Mn][Fe] ZRIKJQADWGOGIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 239000011230 binding agent Substances 0.000 claims description 40
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 claims description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical class [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- 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 discloses a novel potassium ion battery and a preparation method thereof, which utilize a positive active material potassium manganese iron base Prussian white (K)2MnFe(CN)6) Preparing a positive pole piece, preparing a negative pole piece by using a negative active material (S-PAN), wherein the capacity ratio of the negative pole piece to the positive pole piece is 1.05: 1-1.2: 1, and a potassium ion battery assembled by the positive pole piece and the negative pole piece by using an electrolyte has excellent electrochemical performance and can show the electrochemical performance of 290Wh/kg (based on positive and negative electrodes)The sum of the mass of the active materials) and has excellent rate performance and long cycle stability, and can stably cycle for 800 cycles at a current density of 300 mA/g.
Description
Technical Field
The invention relates to the technical field of potassium ion battery preparation, in particular to a novel potassium ion battery and a preparation method thereof.
Background
At present, high-performance lithium ion batteries have been widely used in the fields of mobile electronic devices, electric vehicles, and the like. However, factors such as limited lithium storage and uneven distribution are expected to increase the cost of the lithium ion battery in the future, which greatly limits the application of the lithium ion battery in low-cost and large-scale energy storage scenarios. Therefore, the development of new rechargeable battery systems with low cost and high performance is one of the current research focuses.
Potassium and lithium belong to the alkali metal family, and they have similar physicochemical properties. The potassium ion battery has the advantages of rich potassium reserves, wide sources and low cost, and the characteristics can meet the requirement of large-scale energy storage scenes on low cost of an energy storage system. However, the reported performance of the potassium ion battery is still not ideal, and the reported performance of the potassium ion battery has the problems of low energy density, poor cycle stability, high electrode material cost and the like, and is difficult to meet the requirements of large-scale energy storage scenes on low cost and high performance of an energy storage system.
The cycle life of a battery is mainly determined by the cycle stability of the positive and negative electrode materials constituting the battery. In the aspect of the anode material, the commonly used anode materials comprise prussian blue, polyanion and layered oxide, and the materials have the problems of poor cycle stability, short cycle, insufficient content of extractable potassium ions and the like. In the aspect of negative electrode materials, graphite is widely used at present, and the problems that a potassium ion battery assembled based on a graphite negative electrode has poor charge-discharge rate performance, short cycle period and the like are caused by the slow dynamic performance, the small potassium storage specific capacity and the poor cycle stability of the graphite negative electrode.
Therefore, the method has important significance in finding the potassium ion battery anode material with high potassium storage specific capacity, quick charge and discharge performance, long service life and low cost.
Disclosure of Invention
In view of the above, the invention provides a novel potassium ion battery and a preparation method thereof, and aims to solve the main problems of low energy density, short cycle life and the like of the potassium ion battery caused by the factors such as low specific capacity and poor cycle stability of the negative electrode material of the current potassium ion battery, so as to prepare the novel potassium ion battery which is assembled based on the positive electrode active material potassium manganese iron based prussian white and the negative electrode active material sulfurized polyacrylonitrile and has high energy density and long cycle life.
The invention provides a novel potassium ion battery, which comprises a positive pole piece, potassium ion battery electrolyte and a negative pole piece,
the positive pole piece comprises conductive carbon, a binder and a positive active material, wherein the positive active material is potassium manganese iron-based Prussian white;
the negative pole piece comprises conductive carbon, a binder and a negative active material, wherein the negative active material is vulcanized polyacrylonitrile.
In a possible implementation manner, in the novel potassium ion battery provided by the invention, the mass ratio of the positive active material potassium manganese iron based prussian white in the positive pole piece is 70 wt.% to 95 wt.%;
the total proportion of the conductive carbon and the binder in the positive pole piece is 30-5 wt.%;
the loading capacity of the potassium manganese iron based Prussian white serving as the positive electrode active material is 1mg/cm2～10mg/cm2。
In a possible implementation manner, in the novel potassium ion battery provided by the invention, the mass ratio of the negative active material, namely the vulcanized polyacrylonitrile, in the negative pole piece is 70 wt.% to 95 wt.%;
the total proportion of the conductive carbon and the binder in the negative pole piece is 30-5 wt.%;
the loading capacity of the negative active material vulcanized polyacrylonitrile is 1mg/cm2～10mg/cm2。
In a possible implementation manner, in the novel potassium ion battery provided by the invention, the capacity ratio of the negative electrode plate to the positive electrode plate is 1.05: 1-1.2: 1.
In a possible implementation manner, in the novel potassium ion battery provided by the present invention, the conductive carbon used in the positive electrode plate and the negative electrode plate is one or more of acetylene black, ketjen black, carbon nanotubes, and graphene.
In a possible implementation manner, in the novel potassium ion battery provided by the invention, the binder used in the positive electrode plate is polyvinylidene fluoride or polytetrafluoroethylene.
In a possible implementation manner, in the novel potassium ion battery provided by the invention, the binder used in the negative electrode plate is any one of sodium carboxymethylcellulose, sodium alginate, polyvinylidene fluoride and polytetrafluoroethylene.
In one possible implementation manner, in the novel potassium ion battery provided by the invention, the electrolyte of the potassium ion battery consists of electrolyte salt and a first solvent; wherein the content of the first and second substances,
the electrolyte salt is one or more of potassium hexafluorophosphate, potassium bifluorosulfonyl imide, potassium trifluoromethanesulfonate and potassium bistrifluoromethylsulfonyl imide;
the first solvent is one of carbonates, ethers, trimethyl phosphate and triethyl phosphate.
In a possible implementation manner, in the novel potassium ion battery provided by the invention, the potassium ion battery comprises a button cell battery and a soft package battery.
The invention also provides a preparation method of the novel potassium ion battery, which comprises the following steps:
s1: mixing conductive carbon, a binder and a positive active material potassium manganese iron base Prussian white according to a first preset proportion, adding a second solvent, uniformly stirring, uniformly coating on an aluminum foil current collector, and performing vacuum drying to obtain a positive pole piece;
s2: mixing conductive carbon, a binder and a negative active material, namely polyacrylonitrile sulfide according to a second preset proportion, adding a third solvent, uniformly stirring, uniformly coating on an aluminum foil current collector or a copper foil current collector, and performing vacuum drying to obtain a negative pole piece;
s3: and assembling the positive pole piece, the potassium ion battery electrolyte and the negative pole piece into a potassium ion battery in a glove box with water and oxygen contents lower than 0.1 ppm.
The novel potassium ion battery and the preparation method thereof utilize a positive active material potassium manganese iron base Prussian white (K)2MnFe(CN)6) The method comprises the steps of preparing a positive pole piece, preparing the negative pole piece by using a negative active material, namely vulcanized polyacrylonitrile (S-PAN), wherein the capacity ratio of the negative pole piece to the positive pole piece is 1.05: 1-1.2: 1, and a potassium ion battery assembled by using an electrolyte has excellent electrochemical performance, can show the energy density of 290Wh/kg (based on the sum of the mass of the positive active material and the mass of the negative active material), has excellent rate performance and long cycle stability, can stably cycle for 800 cycles at the current density of 300mA/g, and is simple in synthesis, low in cost, environment-friendly, simple in process of the whole preparation process and low in reaction energy consumption.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a novel potassium ion battery provided by the invention;
FIG. 2 is a graph showing the cycle stability of potassium manganese iron based Prussian white, which is a positive electrode active material in example 1 of the present invention, at a current density of 400 mA/g;
FIG. 3 is a scanning electron microscope photograph of polyacrylonitrile sulfide as a negative active material in example 1 of the present invention;
FIG. 4 is a graph of the cycling stability of polyacrylonitrile sulfide, which is a negative active material, at a current density of 400mA/g in example 1 of the present invention;
FIG. 5 is a graph showing the charge and discharge curves of the potassium ion battery prepared in example 1 of the present invention for the first 3 cycles at a current density of 15 mA/g;
FIG. 6 is a graph showing the cycle stability of the potassium ion battery prepared in example 1 of the present invention at a current density of 300 mA/g.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only illustrative and are not intended to limit the present invention.
The invention provides a novel potassium ion battery, which comprises a positive pole piece, potassium ion battery electrolyte and a negative pole piece; the positive pole piece comprises conductive carbon, a binder and a positive active material, wherein the positive active material is potassium manganese iron-based Prussian white; the negative pole piece comprises conductive carbon, a binder and a negative active material, wherein the negative active material is vulcanized polyacrylonitrile.
In specific implementation, in the novel potassium ion battery provided by the invention, preferably, the mass ratio of the positive active material potassium manganese iron based prussian white in the positive electrode sheet is 70 wt.% to 95 wt.%, and the total ratio (mass ratio) of the conductive carbon and the binder in the positive electrode sheet is 30 wt.% to 5 wt.%. For example, the mass ratio of the positive active material potassium manganese iron based prussian white in the positive electrode sheet is 70 wt.%, and the total ratio (mass ratio) of the conductive carbon and the binder in the positive electrode sheet is 30 wt.%. In a word, the sum of the mass ratios of the conductive carbon, the binder and the positive electrode active material potassium-manganese-iron-based Prussian white is ensured to be 1. The loading capacity of the potassium manganese iron based Prussian white serving as the positive electrode active material can be controlled to be 1mg/cm2～10mg/cm2And (3) a range.
In specific implementation, in the novel potassium ion battery provided by the invention, preferably, the mass ratio of the negative active material polyacrylonitrile sulfide in the negative electrode plate is 70 wt.% to 95 wt.%, and the total ratio (mass ratio) of the conductive carbon and the binder in the negative electrode plate is 30 wt.% to 5 wt.%. For example, the mass ratio of the negative active material polyacrylonitrile sulfide in the negative electrode sheet is 80 wt.%, and the total ratio (mass ratio) of the conductive carbon and the binder in the negative electrode sheet is 20 wt.%. In a word, the sum of the mass ratios of the conductive carbon, the binder and the negative electrode active material vulcanized polyacrylonitrile is ensured to be 1. The loading capacity of the negative active material, namely the vulcanized polyacrylonitrile can be controlled to be 1mg/cm2～10mg/cm2And (3) a range.
In specific implementation, in the novel potassium ion battery provided by the invention, the capacity ratio of the negative electrode plate to the positive electrode plate can be controlled within the range of 1.05: 1-1.2: 1. Of negative and positive electrode platesThe calculation formula of the capacity ratio is
Wherein Q isNegative poleDenotes the capacity, Q, of the negative electrode sheetIs justRepresents the capacity of the positive electrode sheet, mNegative poleRepresents the mass of the negative active material, sulfurized polyacrylonitrile, mIs justThe mass of the positive electrode active material potassium manganese iron based prussian white is shown. Because the surface areas of the positive pole piece and the negative pole piece are the same, the mass ratio of the negative active material sulfurized polyacrylonitrile on the negative pole piece to the positive active material potassium manganese iron base Prussian white on the positive pole piece is the ratio of the negative active material sulfurized polyacrylonitrile on the negative pole piece to the positive active material potassium manganese iron base Prussian white on the positive pole piece.
In specific implementation, in the novel potassium ion battery provided by the invention, the conductive carbon used in the positive electrode plate and the negative electrode plate can be one or more of acetylene black, ketjen black, carbon nanotubes and graphene. The positive electrode piece and the negative electrode piece may use the same conductive carbon, or the positive electrode piece and the negative electrode piece may also use two different conductive carbons, which is not limited herein.
In specific implementation, in the novel potassium ion battery provided by the invention, the binder used in the positive electrode plate can be polyvinylidene fluoride (PVDF); alternatively, the binder used in the positive electrode sheet may also be Polytetrafluoroethylene (PTFE); and are not limited herein.
In specific implementation, in the novel potassium ion battery provided by the invention, the binder used in the negative electrode plate can be sodium carboxymethyl cellulose; or the adhesive used in the negative pole piece can also be sodium alginate; or, the binder used in the negative electrode plate can also be polyvinylidene fluoride (PVDF); or, the adhesive used in the negative electrode plate can also be Polytetrafluoroethylene (PTFE); and are not limited herein.
In specific implementation, in the novel potassium ion battery provided by the invention, the electrolyte of the potassium ion battery can be selected to be composed of electrolyte salt and a first solvent; wherein the electrolyte salt may be sixPotassium Fluophosphate (KPF)6) One or more of potassium bis (fluorosulfonyl) imide salt (KFSI), potassium trifluoromethanesulfonate (KOTf), and potassium bis (trifluoromethanesulfonyl) imide (KTFSI); the first solvent may be any one of carbonates, ethers, trimethyl phosphate (TMP) and triethyl phosphate (TEP), and is not limited thereto.
The novel potassium ion battery provided by the invention may be a button-type potassium ion battery, or may also be a soft-package potassium ion battery, which is not limited herein.
Based on the same inventive concept, the invention also provides a preparation method of the novel potassium ion battery, as shown in fig. 1, comprising the following steps:
s1: mixing conductive carbon, binder and positive active material potassium manganese iron base Prussian white (K)2MnFe(CN)6) Mixing according to a first preset proportion, adding a second solvent, uniformly stirring, uniformly coating on an aluminum foil current collector, and performing vacuum drying to obtain a positive pole piece;
s2: mixing conductive carbon, a binder and a negative active material, namely, vulcanized polyacrylonitrile (S-PAN) according to a second preset proportion, adding a third solvent, uniformly stirring, uniformly coating on an aluminum foil current collector or a copper foil current collector, and drying in vacuum to obtain a negative pole piece;
s3: and assembling the positive pole piece, the potassium ion battery electrolyte and the negative pole piece into the potassium ion battery in a glove box with water and oxygen contents lower than 0.1 ppm.
In specific implementation, in the preparation method of the novel potassium ion battery provided by the invention, when the binder used in the positive electrode plate is polyvinylidene fluoride (PVDF), the second solvent is N-methylpyrrolidone; when the binder used in the positive electrode sheet is Polytetrafluoroethylene (PTFE), the second solvent is isopropanol.
In specific implementation, in the preparation method of the novel potassium ion battery provided by the invention, when the binder used in the negative electrode plate is sodium carboxymethyl cellulose, the third solvent is water; when the binder used in the negative pole piece is sodium alginate, the third solvent is water; when the binder used in the negative electrode plate is polyvinylidene fluoride (PVDF), the third solvent is N-methyl pyrrolidone; when the binder used in the negative electrode sheet is Polytetrafluoroethylene (PTFE), the third solvent is isopropanol.
In addition, in the step S1 of the method for manufacturing the novel potassium ion battery according to the present invention, the conductive carbon, the binder, and the positive electrode active material potassium manganese iron based prussian white (K) are mixed2MnFe(CN)6) And (3) after mixing according to the first preset proportion, adding a second solvent, and uniformly stirring, wherein the mixture and the second solvent have no definite proportion, and the mixture is only required to be uniformly stirred to be in a slurry state. Also, in the step S2 of the method for manufacturing the novel potassium ion battery according to the present invention, after the conductive carbon, the binder, and the negative electrode active material polyacrylonitrile sulfide (S-PAN) are mixed according to a second predetermined ratio, the third solvent is added and stirred uniformly, and the mixture and the third solvent do not have a certain ratio, so long as they are stirred uniformly to form a slurry.
The following provides a detailed description of the specific implementation of the method for manufacturing the novel potassium ion battery provided by the present invention, taking the preparation of the button-type potassium ion battery as an example.
The first step is as follows: mixing the positive active material potassium manganese iron based Prussian white (K)2MnFe(CN)6) Mixing conductive carbon Keqin black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 7:2:1, adding N-methyl pyrrolidone, uniformly stirring, uniformly coating on an aluminum foil current collector, and drying in vacuum at 100 ℃ to obtain a positive electrode plate, wherein the loading capacity of a positive active material is 5mg/cm2。
The second step is that: mixing a negative active material of polyacrylonitrile sulfide (S-PAN), conductive carbon Ketjen black and a binder of sodium carboxymethyl cellulose in a mass ratio of 8:1:1, adding water, uniformly stirring, uniformly coating on an aluminum foil current collector, and drying in vacuum at 100 ℃ to obtain a negative pole piece, wherein the loading capacity of the negative active material is 1.5mg/cm2. And obtaining the capacity ratio of the negative pole piece to the positive pole piece to be 1.06:1 according to a capacity ratio calculation formula of the negative pole piece and the positive pole piece.
The third step: an electrolyte system (2.5M KFSI-TEP) in which potassium bis-fluorosulfonylimide (KFSI) having a composition of 2.5mol/L was dissolved in triethyl phosphate (TEP) was used as a potassium ion battery electrolyte.
The fourth step: and in a glove box with water and oxygen contents lower than 0.1ppm, assembling the button potassium ion battery by using the positive pole piece, the negative pole piece and the potassium ion battery electrolyte.
The morphology of the negative active material, polyacrylonitrile sulfide (S-PAN), was characterized using a Scanning Electron Microscope (SEM), and the cycling stability of the positive active material, the negative active material, and the assembled full cell was characterized using a constant current charge-discharge test method.
FIG. 2 shows a positive electrode active material potassium manganese iron based Prussian white (K) in example 1 of the present invention2MnFe(CN)6) The cycle stability graph under the current density of 400mA/g can be seen from figure 2, the discharge capacity of the 1 st circle is 81mA/g, the discharge capacity of the 1500 th circle is 77.7mA/g, therefore, the capacity retention rate of 95.9% can be still obtained after 1500 cycles, and the result shows that the potassium manganese iron based Prussian white (K) as the positive electrode active material is2MnFe(CN)6) Has excellent cycle stability. Fig. 3 is a Scanning Electron Microscope (SEM) image of polyacrylonitrile sulfide (S-PAN) as the negative active material in example 1 of the present invention, and it can be seen from fig. 3 that polyacrylonitrile sulfide (S-PAN) as the negative active material exhibits a random spherical morphology, and the particle size is between 100nm and 200 nm. Fig. 4 is a graph of the cycling stability of the negative active material polyacrylonitrile sulfide (S-PAN) in example 1 of the present invention at a current density of 400mA/g, and it can be seen from fig. 4 that the discharge capacity at the 1 st cycle is 391.3mA/g, the capacity of the polyacrylonitrile sulfide gradually increases during the cycling process, and the capacity is 435mA/g after 440 cycles, which shows that the polyacrylonitrile sulfide (S-PAN) has a good cycling stability when used as the negative active material of a potassium ion battery. FIG. 5 is a charging and discharging graph of the potassium ion battery prepared in example 1 of the present invention at a current density of 15mA/g for the first 3 cycles, and it can be seen from FIG. 5 that based on potassium manganese iron based Prussian white (K)2MnFe(CN)6) Potassium ion batteries assembled with positive electrodes, polyacrylonitrile sulfide (S-PAN) negative electrodes, and 2.5M KFSI-TEP electrolyte systems can exhibit 150.7mAh/g (based on positive electrode active material)Mass), corresponding to an energy density of up to 290Wh/kg (based on the sum of the masses of the positive and negative active materials). Fig. 6 is a cycle stability graph of the potassium ion battery prepared in example 1 of the present invention at a current density of 300mA/g, and it can be seen from fig. 6 that the potassium ion battery prepared in example 1 of the present invention exhibits excellent cycle stability, the discharge capacity at the 1 st cycle at the current density of 300mA/g is 93.1mA/g, the discharge capacity after 800 cycles is 86.7mA/g, and the capacity retention rate is as high as 93.1%.
The novel potassium ion battery and the preparation method thereof utilize a positive active material potassium manganese iron base Prussian white (K)2MnFe(CN)6) The method comprises the steps of preparing a positive pole piece, preparing the negative pole piece by using a negative active material, namely vulcanized polyacrylonitrile (S-PAN), wherein the capacity ratio of the negative pole piece to the positive pole piece is 1.05: 1-1.2: 1, and a potassium ion battery assembled by using an electrolyte has excellent electrochemical performance, can show the energy density of 290Wh/kg (based on the sum of the mass of the positive active material and the mass of the negative active material), has excellent rate performance and long cycle stability, can stably cycle for 800 cycles at the current density of 300mA/g, and is simple in synthesis, low in cost, environment-friendly, simple in process of the whole preparation process and low in reaction energy consumption.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A novel potassium ion battery comprises a positive pole piece, potassium ion battery electrolyte and a negative pole piece, and is characterized in that the positive pole piece is connected with the electrolyte;
the positive pole piece comprises conductive carbon, a binder and a positive active material, wherein the positive active material is potassium manganese iron-based Prussian white;
the negative pole piece comprises conductive carbon, a binder and a negative active material, wherein the negative active material is vulcanized polyacrylonitrile.
2. The novel potassium ion battery as claimed in claim 1, wherein the positive active material potassium manganese iron based prussian white accounts for 70 wt.% to 95 wt.% in the positive electrode sheet;
the total proportion of the conductive carbon and the binder in the positive pole piece is 30-5 wt.%;
the loading capacity of the potassium manganese iron based Prussian white serving as the positive electrode active material is 1mg/cm2～10mg/cm2。
3. The novel potassium ion battery of claim 1, wherein the negative active material polyacrylonitrile sulfide in the negative pole piece accounts for 70 wt.% to 95 wt.%;
the total proportion of the conductive carbon and the binder in the negative pole piece is 30-5 wt.%;
the loading capacity of the negative active material vulcanized polyacrylonitrile is 1mg/cm2～10mg/cm2。
4. The novel potassium ion battery of claim 1, wherein the capacity ratio of the negative electrode sheet to the positive electrode sheet is 1.05:1 to 1.2: 1.
5. The novel potassium ion battery of claim 1, wherein the conductive carbon used in the positive electrode sheet and the negative electrode sheet is one or more of acetylene black, ketjen black, carbon nanotubes, and graphene.
6. The novel potassium ion battery as claimed in claim 1, wherein the binder used in the positive electrode plate is polyvinylidene fluoride or polytetrafluoroethylene.
7. The novel potassium ion battery as claimed in claim 1, wherein the binder used in the negative electrode plate is any one of sodium carboxymethylcellulose, sodium alginate, polyvinylidene fluoride and polytetrafluoroethylene.
8. The novel potassium ion battery of claim 1 wherein the potassium ion battery electrolyte is comprised of an electrolyte salt and a first solvent; wherein the content of the first and second substances,
the electrolyte salt is one or more of potassium hexafluorophosphate, potassium bifluorosulfonyl imide, potassium trifluoromethanesulfonate and potassium bistrifluoromethylsulfonyl imide;
the first solvent is one of carbonates, ethers, trimethyl phosphate and triethyl phosphate.
9. The novel potassium ion battery according to any one of claims 1-8, wherein the potassium ion battery comprises a button cell battery and a pouch cell battery.
10. A method for preparing a novel potassium ion battery according to any one of claims 1 to 9, comprising the steps of:
s1: mixing conductive carbon, a binder and a positive active material potassium manganese iron base Prussian white according to a first preset proportion, adding a second solvent, uniformly stirring, uniformly coating on an aluminum foil current collector, and performing vacuum drying to obtain a positive pole piece;
s2: mixing conductive carbon, a binder and a negative active material, namely polyacrylonitrile sulfide according to a second preset proportion, adding a third solvent, uniformly stirring, uniformly coating on an aluminum foil current collector or a copper foil current collector, and performing vacuum drying to obtain a negative pole piece;
s3: and assembling the positive pole piece, the potassium ion battery electrolyte and the negative pole piece into a potassium ion battery in a glove box with water and oxygen contents lower than 0.1 ppm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114864298A (en) * | 2022-04-11 | 2022-08-05 | 山东大学 | Water-based potassium ion electrolyte and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018123487A1 (en) * | 2016-12-26 | 2018-07-05 | 学校法人東京理科大学 | Positive electrode active material for potassium-ion cell, positive electrode for potassium-ion cell, and potassium-ion cell |
| CN109065847A (en) * | 2018-05-25 | 2018-12-21 | 浙江大学 | A kind of white composite material and preparation method in Prussia and application |
| CN110002465A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of white analog positive electrode in Prussia, preparation method and application |
| CN110400963A (en) * | 2018-05-14 | 2019-11-01 | 宁波致轻电池有限公司 | A kind of metallic sodium or Na-K alloy cathode/sulfurized polyacrylonitrile anode secondary cell and its manufacturing method |
-
2021
- 2021-04-07 CN CN202110373512.2A patent/CN113161603A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018123487A1 (en) * | 2016-12-26 | 2018-07-05 | 学校法人東京理科大学 | Positive electrode active material for potassium-ion cell, positive electrode for potassium-ion cell, and potassium-ion cell |
| CN110400963A (en) * | 2018-05-14 | 2019-11-01 | 宁波致轻电池有限公司 | A kind of metallic sodium or Na-K alloy cathode/sulfurized polyacrylonitrile anode secondary cell and its manufacturing method |
| CN109065847A (en) * | 2018-05-25 | 2018-12-21 | 浙江大学 | A kind of white composite material and preparation method in Prussia and application |
| CN110002465A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of white analog positive electrode in Prussia, preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114864298A (en) * | 2022-04-11 | 2022-08-05 | 山东大学 | Water-based potassium ion electrolyte and preparation method and application thereof |
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