CN117673484A - Potassium-based double-ion battery based on tellurium cathode and preparation method thereof - Google Patents
Potassium-based double-ion battery based on tellurium cathode and preparation method thereof Download PDFInfo
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 69
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 34
- 239000011591 potassium Substances 0.000 title claims abstract description 34
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 46
- 239000010439 graphite Substances 0.000 claims abstract description 46
- 239000006184 cosolvent Substances 0.000 claims abstract description 31
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000011149 active material Substances 0.000 claims abstract description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 30
- 239000004917 carbon fiber Substances 0.000 claims description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- -1 tellurium selenide Chemical class 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000007770 graphite material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000002391 graphite-based active material Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003064 anti-oxidating effect Effects 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 4
- 210000004027 cell Anatomy 0.000 claims 3
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims 2
- 210000002777 columnar cell Anatomy 0.000 claims 1
- 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 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XLRGLCLTYMKRRJ-UHFFFAOYSA-N [K].FS(=N)F Chemical compound [K].FS(=N)F XLRGLCLTYMKRRJ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Abstract
The invention belongs to the technical field of electrochemistry, and particularly relates to a tellurium-cathode-based potassium-based double-ion battery and a preparation method thereof. The potassium-based double-ion battery comprises a self-supporting tellurium-based negative electrode, fluorinated cosolvent modified ester-based electrolyte and a graphite positive electrode. The preparation method comprises the following steps: preparing tellurium-based negative electrode, preparing electrolyte, preparing graphite positive plate and assembling battery. The tellurium-based anode is characterized by self-supporting, avoids the use of current collectors and the like, has higher conversion reaction potential of tellurium-based active materials, and can prevent potassium precipitation of the anode. In addition, by balancing the concentration and the content of the fluorinated cosolvent, the efficient anion storage of the graphite anode is realized on the premise of high voltage stability of the electrolyte. The double-ion battery provided by the invention has the advantages of light structure, reasonable design, high safety, higher working voltage and energy density and stable cycle performance.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a tellurium-cathode-based potassium-based double-ion battery and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) are widely applied to the fields of various electronic products, electric automobiles and the like, but lithium sources in the crust are limited and unevenly distributed, the LIBs face the problem that the manufacturing cost is continuously increased, and development of novel energy storage devices capable of replacing the LIBs is imperative. Double Ion Batteries (DIBs) are a class of energy storage devices that have high operating voltages, wide temperature ranges, and high power densities, employ cobalt-free electrode materials, and are environmentally friendly. Unlike the rocking chair type operation mechanism of lithium ion battery, the double ion battery has its negative and positive ions inserted into and separated from the positive and negative electrodes during the charge/discharge process. Compared with lithium, the potassium resource is more abundant; compared with sodium (-2.71V), the standard electrode potential of potassium is lower (-2.93V), so that the potassium-based double-ion battery (KDIBs) has higher energy density, and has better application prospect in the fields of large-scale energy storage and the like.
The cost and electrochemical performance of a bi-ionic cell depend primarily on the electrode materials and electrolyte. Currently, little research is done on kdbs anode materials. The soft carbon and graphite negative electrode has lower specific capacity and unsatisfactory multiplying power performance when potassium ions are stored, and lower discharge potential brings about potential safety hazards of potassium precipitation. In recent years, simple substance tellurium (Te) has high specific volume capacity, moderate voltage plateau and high conductivity (2×10) 2 S m -1 ) Is a very potential negative electrode material, which is attracting attention. Unlike the same-group elements sulfur and selenium, tellurium has a larger atomic radius, limiting the formation of soluble intermediate-polytelluride, the shuttle effect has less impact, but due to K + The large ionic radius of the tellurium-based anode material causes larger volume change and irreversible structural damage in the charge and discharge process, and the cycle stability is poor. Most of tellurium-based anode materials prepared in the past are in powder form, and a mixed binder and a conductive agent are needed for use, so that the electrode active material proportion is reduced, the dead quality of a battery is increased by using a copper current collector of the anode, and the energy density is greatly reduced. Therefore, development of the self-supporting tellurium-based anode is expected to further improve the energy density of KDIbs. For the positive electrode, the organic matters and the metal organic frame positive electrode have low normal working voltage and poor cycle performance; graphite is low in price, can be used as a KDIbs positive electrode to reduce the manufacturing cost of a battery, has high working voltage and potential of high energy density during anion intercalation, and brings great challenges to electrochemical stability of electrolyte. Because the high voltage tolerance of the conventional carbonate organic electrolyte is poor, the graphite anode has lower specific capacity, and the large volume change during intercalation/deintercalation of large-size anions easily causes stripping of a graphite layer and poor cycle performance; although high concentrations of carbonate-based electrolytes and sulfone-based electrolytes can significantly improve the cycle life and specific capacity of graphite positive electrode-based kdbs, the cost-effectiveness of the battery is impaired. Fluorinated solvents have a lower highest occupied molecular orbital energy level and are resistant to oxidation compared to fluorine-free solventsThe solution has stronger capability, can widen the electrochemical stability window of the electrolyte by taking the solution as a cosolvent, has weaker solvation capability of the fluorinated solvent and can reduce the concentration of the electrolyte. Therefore, balancing the concentration of the ester-based electrolyte and the amount of fluorinated cosolvent is an important means for achieving both high voltage stability and cost of the electrolyte.
Therefore, the invention provides a potassium-based double-ion battery based on tellurium cathode and a preparation method thereof, wherein an electrostatic spinning technology-a high-temperature calcination method is adopted to prepare a self-supporting tellurium-based cathode, commercial graphite materials are used as positive electrode active substances, fluorinated cosolvent modified ester-based electrolyte is matched, the concentration of the electrolyte and the consumption of the fluorinated cosolvent are balanced, and an interfacial film rich in potassium fluoride (KF) is constructed on the premise of ensuring high voltage stability so as to relieve the volume change of graphite during intercalation/deintercalation of anions, so that KDIBs show high safety, high working voltage, high energy density and stable cycle performance.
Disclosure of Invention
The invention aims to provide a potassium-based double-ion battery based on a tellurium cathode and a preparation method thereof.
The invention further aims to provide a potassium-based double-ion battery based on a tellurium negative electrode and a preparation method thereof, wherein the preparation method adopts the fluorinated cosolvent modified ester-based electrolyte, so that the concentration of the electrolyte is reduced to the greatest extent on the premise of ensuring high-voltage stability, the cost is saved, and meanwhile, an interfacial film rich in KF is constructed on a graphite positive electrode to inhibit volume expansion of a graphite active material in a circulating process.
The third object of the invention is to provide a potassium-based double-ion battery based on a self-supporting tellurium-based negative electrode, a fluorinated cosolvent modified ester-based electrolyte and a graphite-based positive electrode, so that the potassium-based double-ion battery has excellent electrochemical performance and high safety.
The self-supporting tellurium-based anode consists of a tellurium-based active material and porous carbon fibers, wherein the tellurium-based active material comprises one or more of tellurium, tellurium sulfide and tellurium selenide, and preferably tellurium.
The fluorinated cosolvent modified ester-based electrolyte consists of potassium salt, an ester solvent and a fluorinated cosolvent, wherein the potassium salt comprises one or more of potassium tetrafluoroborate, potassium hexafluorophosphate, potassium trifluoromethane sulfonate, potassium perchlorate, potassium bis-fluorosulfonyl imide and potassium bis-trifluoromethane sulfonyl imide, preferably potassium bis-fluorosulfonyl imide, the ester solvent comprises one or more of carbonates, phosphates, carboxylates and sulfites, preferably the phosphate solvent, and the fluorinated cosolvent comprises one or more of fluorinated carbonates, fluorinated phosphates, fluorinated ethers, fluorinated carboxylates and fluorinated sulfites, preferably the fluorinated phosphate cosolvent.
The commercialized graphite material comprises one or more of high-purity crystalline flake graphite, natural graphite, ketjen black, expanded graphite, mesophase carbon microspheres, graphene and high-orientation graphite, and is preferably high-purity crystalline flake graphite.
The potassium-based double-ion battery based on the tellurium cathode is one of a button battery, a soft-package battery and a columnar battery, preferably a button battery, and the capacity ratio (N/P value) of the self-supporting tellurium cathode to the graphite cathode is 1.1-1.5, preferably 1.1.
The invention provides a potassium-based double-ion battery based on tellurium cathodes and a preparation method thereof, which are characterized by being realized by the following technical scheme:
(1) Self-supporting tellurium-based anode preparation: polyacrylonitrile (PAN) is taken as a carbon source, polystyrene (PS) is taken as a pore-forming agent to be dissolved in N, N-Dimethylformamide (DMF) together, a precursor solution is obtained, and the PS/PAN nanofiber film is prepared through an electrostatic spinning process; placing the film into a tube furnace, and preparing porous carbon fibers through low-temperature pre-oxidation and high-temperature carbonization processes; then putting commercial tellurium powder or one or two of selenium powder and sulfur powder and the porous carbon fiber into a tube furnace together, and preparing a self-supporting tellurium-based negative electrode through a high-temperature melting-diffusion process in an inert gas atmosphere; finally, cutting the battery into proper electrode plates according to different battery structure types, and directly taking the electrode plates as the negative electrode of the KDIbs.
(2) Preparing an electrolyte: mixing potassium salt and an ester solvent in a glove box in a high-purity argon atmosphere, uniformly stirring, then adding fluorinated cosolvent with different contents as a diluent, controlling the volume ratio of the ester solvent to the fluorinated cosolvent to be 1:1-20:1, and uniformly stirring to obtain the fluorinated cosolvent modified ester-based electrolyte.
(3) Preparing a graphite positive electrode: mixing one or more of commercial graphite materials including high-purity flake graphite, natural graphite, ketjen black, expanded graphite, mesophase carbon microspheres, graphene and high-orientation graphite with a conductive agent Super P and a binder sodium carboxymethyl cellulose, grinding uniformly, adding a dispersing agent deionized water, stirring into slurry, coating on an aluminum current collector, and vacuum drying to prepare the graphite anode, wherein the mass fraction of the graphite active material is 80% -95%.
(4) Potassium-based double-ion battery assembly based on tellurium cathode: and assembling KDIBs based on the self-supporting tellurium cathode, the graphite anode and the fluorinated cosolvent modified ester-based electrolyte in a glove box in a high-purity argon atmosphere.
The invention has the advantages and positive effects that:
the invention obtains a potassium-based double-ion battery based on tellurium cathodes and a preparation method thereof through ingenious electrode structure design and electrolyte optimization strategies. The prepared self-supporting tellurium-based anode avoids the use of conductive agents, binders and copper current collectors, reduces the weight of the battery, is beneficial to improving the energy density, and a moderate voltage platform can prevent potassium precipitation of the anode in KDIbs; compared with the high-concentration ester-based electrolyte, the introduction of the fluorinated cosolvent reduces the cost of the electrolyte to the maximum extent on the premise of ensuring a wider electrochemical stability window of the electrolyte, and is further matched with a commercial graphite anode with low cost, and an interfacial film rich in KF is constructed on the surface of the electrolyte to inhibit volume expansion in the circulation process, so that the efficient anion storage of the graphite anode is realized. Under the synergistic effect, the fluorinated cosolvent modified ester-based electrolyte can enable KDIBs based on tellurium cathodes to have high safety, high working voltage, high energy density and stable cycle performance, and the practicability of the DIBs is promoted.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a self-supporting tellurium@porous carbon fiber negative electrode prepared in example 1;
FIG. 2 is a view of a self-supporting tellurium@porous carbon fiber negative electrode Transmission Electron Microscope (TEM) prepared in example 1;
FIG. 3 is a Linear Sweep Voltammetry (LSV) plot of K/Al cells of potassium bis-fluorosulfonyl imide (KFSI)/triethyl phosphate (TEP) -FTEP electrolyte based on varying amounts of tris (2, 2-trifluoroethyl) phosphate (FTEP) in example 1;
FIG. 4 is a graph of 3.0 to 5.25V (vs. K) for KFSI/TEP-FTEP electrolytes with varying fluorinated co-solvent levels in example 1 + K) voltage range and 200mAg -1 A charge-discharge curve of the high-purity flake graphite anode under current density;
FIG. 5 shows the KFSI/5 TEP-FTEP-based electrolyte of example 1 at 0.01-3.0V (vs. K + K) voltage range and 200mAg -1 A charge-discharge curve of the self-supporting tellurium@porous carbon fiber cathode under current density;
FIG. 6 shows KDIbs based on self-supporting tellurium@porous carbon fiber anode, high purity flake graphite anode and KFSI/5TEP-FTEP electrolyte in example 1 at a voltage range of 1.0-5.25V and 100mAg -1 A cycle performance curve at current density;
FIG. 7 is a graph of KDIbs based on self-supporting tellurium@porous carbon fiber anode, high purity crystalline flake graphite anode, and KFSI/5TEP-FTEP electrolyte in example 1 at a voltage range of 1.0-5.25V and at different current densities.
Detailed Description
The present invention is described in further detail below by way of specific examples, which will enable those skilled in the art to more fully understand the invention, but are not limited in any way.
Example 1:
the invention provides a potassium-based double-ion battery based on tellurium cathodes and a preparation method thereof. As a preferred example, kdbs based on a self-supporting tellurium@porous carbon fiber anode, KFSI/5TEP-FTEP electrolyte and high purity flake graphite anode were prepared using the following experimental procedure and exhibited excellent electrochemical properties and high safety.
(1) The preparation method of the self-supporting tellurium@porous carbon fiber cathode comprises the following specific processes: 0.5g of Polyacrylonitrile (PAN) as a carbon source and 0.1g of Polystyrene (PS) as a pore-forming agent are dissolved together in 4mL of N, N-Dimethylformamide (DMF), and stirred at room temperature for 24h; the precursor solution is filled into a syringe with a stainless steel nozzle, and the syringe is placed at 15kV voltage and 18cm distance and 8 mu Lmin –1 Preparing a PS/PAN nanofiber film through an electrostatic spinning process at a propulsion speed; then, the film is spread in a square boat, and is filled in a vacuum tube furnace, preoxidation is carried out at the constant temperature of 250 ℃ for 2 hours under the air atmosphere, and high-temperature carbonization is carried out at the constant temperature of 800 ℃ for 2 hours under the argon atmosphere, so as to prepare the porous carbon fiber; then, respectively spreading 100mg tellurium powder and 25mg of the porous carbon fiber at two ends of a square boat, putting the square boat and the porous carbon fiber into a vacuum tube furnace, and preparing the self-supporting tellurium@porous carbon fiber through a fusion-diffusion process under an inert gas atmosphere at a constant temperature of 480 ℃ for 17 hours; finally, cutting the material into a circular sheet with the diameter of 8mm, and directly taking the circular sheet as a negative electrode of button-type KDIBs.
(2) Preparing KFSI/TEP-FTEP electrolyte, which comprises the following specific processes: in a glove box (O) under high purity argon atmosphere 2 <0.01ppm,H 2 O<0.01 ppm), 0.8602g of potassium difluorosulfimide (KFSI) is dissolved in 1mL of triethyl phosphate (TEP), and mixed and stirred for 24 hours to obtain high-concentration KFSI/TEP electrolyte, and 0.5, 0.33, 0.25 and 0.2mL of tris (2, 2-trifluoroethyl) phosphate (FTEP) are respectively added, and after stirring for 12 hours, KFSI/2TEP-FTEP, KFSI/3TEP-FTEP, KFSI/4TEP-FTEP and KFSI/5TEP-FTEP electrolyte are respectively obtained.
(3) The preparation method of the high-purity flake graphite anode comprises the following specific processes: mixing high-purity flake graphite with a conductive agent Super P and a binder sodium carboxymethyl cellulose (CMC) in a mass ratio of 80-10%, manually grinding for 30min, adding deionized water as a dispersing agent to prepare slurry, uniformly coating the slurry on an aluminum sheet with the diameter of 14mm, and vacuum drying at 60 ℃ for 24h to obtain the high-purity flake graphite anode.
(4) The half-cell assembly and performance test are carried out by the following specific processes: KFSI/TEP-FT obtained by the methodEP electrolyte in a glove box (O) 2 <0.01ppm，H 2 O<0.01 ppm), and assembling half batteries based on electrolytes of different compositions, high-purity flake graphite positive electrodes and potassium metal at a voltage of 3.0-5.25V (vs. K) + K) voltage range and 200mAg -1 And (5) acquiring a charge-discharge curve of the electrolyte under the current density, and screening the electrolyte. Then, a half cell based on a negative electrode containing the screened KFSI/5TEP-FTEP electrolyte, self-supporting tellurium@porous carbon fiber and potassium metal was assembled at 0.01-3V (vs K) + Voltage range of/K) and 200mA g -1 The cycle performance was tested at current density.
(5) The potassium-based double-ion battery based on tellurium cathode is assembled and tested in performance, and the specific process is as follows: in a high purity argon glove box (O) 2 <0.01ppm，H 2 O<0.01 ppm), assembling KDIBs based on self-supporting tellurium@porous carbon fiber anode, high-purity crystalline flake graphite anode and screened KFSI/5TEP-FTEP electrolyte, wherein the capacity ratio (N/P value) of the anode to the cathode is controlled to be 1.1, and 100mA g is controlled within the voltage range of 1.0-5.25V -1 The cycle performance was tested at current densities and varied between 100, 200, 300, 400 and 500mAg -1 The charge-discharge curve was tested at current density.
The self-supporting tellurium@porous carbon fiber prepared by the method provided by the invention has a microstructure observed through a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM). And collecting the cycle curves, charge and discharge curves of the half battery and the KDIbs by using a Neware CT-4008 battery tester. An Autolab electrochemical workstation was used to collect Linear Sweep Voltammetry (LSV) curves for K// Al cells based on KFSI/TEP-FTEP electrolytes with different fluorinated co-solvent contents.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a self-supporting tellurium@porous carbon fiber negative electrode prepared in example 1. From the SEM image, it can be seen that the Polystyrene (PS) is used as a pore-forming agent, so that a rich large pore structure can be constructed in the radial direction of the carbon fiber, and tellurium loading and subsequent electrolyte infiltration and mass transfer in the high-temperature melting-diffusion process are facilitated.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the self-supporting tellurium@porous carbon fiber negative electrode prepared in example 1. The TEM image shows that the large pore canal structure is uniformly distributed and penetrates through the radial direction of the whole carbon fiber, and tellurium is uniformly loaded on the porous carbon fiber without aggregation.
FIG. 3 is a Linear Sweep Voltammetry (LSV) plot of K/Al cells of KFSI/TEP-FTEP electrolytes based on varying fluorinated co-solvent content in example 1. From the LSV graph, the highest oxidation potential of the KFSI/TEP-FTEP electrolyte is dominated by concentration and is not FTEP content, wherein the antioxidation potential of the KFSI/5TEP-FTEP electrolyte is as high as 5.35V, and the necessary condition for constructing high working voltage KDIbs is satisfied.
FIG. 4 is a graph of 3.0 to 5.25V (vs. K) for KFSI/TEP-FTEP electrolytes with varying fluorinated co-solvent levels in example 1 + K) voltage range and 200mAg -1 And (3) a charge-discharge curve of the high-purity flake graphite anode under the current density. When the volume ratio of TEP to FTEP in the electrolyte increases from 2:1 to 5:1, the reversible capacity of the graphite positive electrode increases from 53.6 to 67.7mAh g -1 And the median voltage of discharge is as high as 4.57V. By comprehensive comparison, the KFSI/5TEP-FTEP electrolyte has the strongest oxidation resistance, and the use of the KFSI/5TEP-FTEP electrolyte enables the graphite anode to realize high-capacity FSI storage, which is mainly due to the fact that the solvation structure of the KFSI/5TEP-FTEP electrolyte contains a large amount of anion-cation complexes, and the FSI-derived interface film rich in KF can be constructed on the graphite anode, so that the volume change of graphite during intercalation/deintercalation of FSI anions is effectively inhibited.
FIG. 5 shows the KFSI/5 TEP-FTEP-based electrolyte of example 1 at 0.01-3.0V (vs. K + K) voltage range and 200mAg -1 And a charge-discharge curve of the self-supporting tellurium@porous carbon fiber cathode under the current density. From the graph, the discharge voltage platform of the self-supporting tellurium@porous carbon fiber anode is 1.0V, potassium precipitation of the anode can be prevented when the self-supporting tellurium@porous carbon fiber anode is applied to KDIbs, so that the safety of a battery is improved, the cycle performance is stable, and the specific capacity after 1000 circles is as high as 161.8mAh g -1 。
FIG. 6 is a graph showing KDIbs of the self-supporting tellurium@porous carbon fiber anode, high purity flake graphite anode, and KFSI/5TEP-FTEP electrolyte in example 1 at a voltage range of 1.0 to 5.25V and 100mA-g -1 Cycling performance curve at current density. At 100mAg -1 After 110 circles of lower circulation, the specific capacity of KDIBs is maintained at 46.3mAh g -1 。
FIG. 7 is a graph of KDIbs based on self-supporting tellurium@porous carbon fiber anode, high purity crystalline flake graphite anode, and KFSI/5TEP-FTEP electrolyte in example 1 at a voltage range of 1.0-5.25V and at different current densities. As can be seen from the graph, 100mA g -1 The average operating voltage of KDIbs at current density is up to 4.09V, and the current density is increased to 500mA g -1 The average operating voltage of kdbs is still 3.0V.
Claims (6)
1. A potassium-based double-ion battery based on tellurium cathode and a preparation method thereof are characterized in that: a self-supporting tellurium-based negative electrode, a fluorinated cosolvent modified ester-based electrolyte and a graphite positive electrode are adopted to construct a potassium-based double-ion battery (KDIBs) with high safety, high working voltage, high energy density and stable cycle performance.
2. A potassium-based double-ion battery based on tellurium cathode and a preparation method thereof are characterized in that the preparation process comprises the following steps:
(1) Polyacrylonitrile (PAN) is taken as a carbon source, polystyrene (PS) is taken as a pore-forming agent to be dissolved in N, N-Dimethylformamide (DMF) together, a precursor solution is obtained, and the PS/PAN nanofiber film is prepared through an electrostatic spinning process; placing the film into a tube furnace, and preparing porous carbon fibers through low-temperature pre-oxidation and high-temperature carbonization processes; then putting commercial tellurium powder or one or two of selenium powder and sulfur powder and the porous carbon fiber into a tube furnace together, and preparing a self-supporting tellurium-based negative electrode through a high-temperature melting-diffusion process in an inert gas atmosphere; finally, cutting the battery into proper electrode plates according to different battery structure types, and directly serving as a negative electrode of the KDIBs;
(2) In a glove box with high-purity argon atmosphere, mixing and uniformly stirring potassium salt and an ester solvent to obtain a high-concentration ester-based electrolyte, adding a fluorinated cosolvent with high antioxidation capability as a diluent, controlling the volume ratio of the ester solvent to the fluorinated cosolvent to be 1:1-20:1, and uniformly stirring to obtain the fluorinated cosolvent modified ester-based electrolyte;
(3) Mixing a commercial graphite material with a conductive agent Super P and a binder sodium carboxymethyl cellulose, grinding uniformly, adding a dispersing agent deionized water to prepare slurry, uniformly coating the slurry on an aluminum current collector, and vacuum drying to obtain a graphite positive electrode, wherein the mass fraction of the graphite active material is 80% -95%;
(4) And (3) assembling the self-supporting tellurium-based anode obtained in the step (1), the fluorinated cosolvent modified ester-based electrolyte obtained in the step (2) and the graphite anode obtained in the step (3) into a potassium-based double-ion battery based on the tellurium anode in a glove box in a high-purity argon atmosphere.
3. The tellurium-anode-based potassium-based dual ion battery and the preparation method thereof as claimed in claim 2, wherein: the self-supporting tellurium-based anode in the step (1) is composed of a tellurium-based active material and porous carbon fibers, wherein the tellurium-based active material comprises one or more of tellurium, tellurium sulfide and tellurium selenide, and preferably tellurium.
4. The tellurium-anode-based potassium-based dual ion battery and the preparation method thereof as claimed in claim 2, wherein: the fluorinated cosolvent modified ester-based electrolyte in the step (2) consists of potassium salt, an ester solvent and a fluorinated cosolvent, wherein the potassium salt comprises one or more of potassium tetrafluoroborate, potassium hexafluorophosphate, potassium trifluoromethane sulfonate, potassium perchlorate, potassium bis (fluorosulfonyl) imide and potassium bis (trifluoromethane sulfonyl) imide, preferably the potassium bis (fluorosulfonyl) imide), the ester solvent comprises one or more of carbonates, phosphates, carboxylates and sulfites, preferably the phosphate solvent, and the fluorinated cosolvent comprises one or more of fluorinated carbonates, fluorinated phosphates, fluorinated ethers, fluorinated carboxylates and fluorinated sulfites, preferably the fluorinated phosphate cosolvent.
5. The tellurium-anode-based potassium-based dual ion battery and the preparation method thereof as claimed in claim 2, wherein: the commercialized graphite material in the step (3) comprises one or more of high-purity flake graphite, ketjen black, natural graphite, expanded graphite, mesophase carbon microspheres, graphene and high-orientation graphite, and is preferably high-purity flake graphite.
6. The tellurium-anode-based potassium-based dual ion battery and the preparation method thereof as claimed in claim 2, wherein: the configuration of the KDIbs in the step (4) comprises one of a button cell, a soft-pack cell and a columnar cell, preferably a button cell, and the capacity ratio (N/P value) of the self-supporting tellurium-based negative electrode to the graphite-based positive electrode is 1.1-1.5, preferably 1.1.
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