CN114655941A - Zinc phosphide material, zinc phosphide composite material, and preparation method and application thereof - Google Patents
Zinc phosphide material, zinc phosphide composite material, and preparation method and application thereof Download PDFInfo
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- CN114655941A CN114655941A CN202210416127.6A CN202210416127A CN114655941A CN 114655941 A CN114655941 A CN 114655941A CN 202210416127 A CN202210416127 A CN 202210416127A CN 114655941 A CN114655941 A CN 114655941A
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- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000006011 Zinc phosphide Substances 0.000 title claims abstract description 110
- 229940048462 zinc phosphide Drugs 0.000 title claims abstract description 110
- 239000000463 material Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 54
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims abstract description 47
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 26
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000006479 redox reaction Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000012300 argon atmosphere Substances 0.000 claims description 11
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002110 nanocone Substances 0.000 claims description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000007772 electrode material Substances 0.000 abstract description 11
- 230000001351 cycling effect Effects 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229940037179 potassium ion Drugs 0.000 description 20
- 238000012360 testing method Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 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 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical group [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a zinc phosphide material, a zinc phosphide composite material, and a preparation method and application thereof. The zinc phosphide composite material is doped with amorphous zinc phosphate. The preparation method of the zinc phosphide material comprises the following steps: the zinc phosphide material can be obtained by ball milling the mixture of metal zinc, zinc oxide and phosphorus. By doping zinc phosphate in zinc phosphide, the volume expansion of active zinc phosphide in the charge-discharge process can be buffered, the utilization rate of the zinc phosphide material as a potassium ion negative electrode material is improved, and the cycling stability of the electrode material is improved. Through one-step ball milling, the raw materials are subjected to oxidation-reduction reaction to generate zinc phosphide and form zinc phosphate in situ. No other post-treatment is needed, and the method is favorable for large-scale production and use. In addition, the carbon material is mixed and added into the zinc phosphide material to form the composite material as the active material of the negative electrode material of the potassium ion battery, so that the phenomenon of conductivity reduction caused by the existence of zinc phosphate can be compensated.
Description
Technical Field
The invention relates to the technical field of battery electrode materials, in particular to a zinc phosphide material, a zinc phosphide composite material, and a preparation method and application thereof.
Background
The large-scale application of fossil energy (coal, oil and natural gas) brings unprecedented industrialization and information revolution to human beings, so that the human lives are more convenient, however, the problem of environmental pollution caused by the prior art is that the human beings begin to examine the reasonable development and use of the traditional non-renewable fossil energy. In order to change the current situation, it is urgently needed to develop new green energy with little pollution or even no pollution so as to make up for the energy vacancy caused by reducing the use of fossil energy and even meet the ever-increasing energy demand of human development. Currently, these new sustainable energy forms include mainly solar, wind, geothermal and tidal energy, among others. However, limited to the regional, intermittent and seasonal nature of these new energy sources, the premise behind the large scale use of these renewable energy sources in place of traditional fossil energy sources is the construction of large numbers of smart grid systems for energy delivery, storage and distribution. For this reason, a large number of reliable energy storage systems need to be provided.
Compared with other energy storage systems, such as flywheel energy storage, pumped storage, compressed air energy storage and the like, electrochemical energy storage has the characteristics of high efficiency and low cost, and particularly, lithium ion batteries which are commercially used at the end of the last century are widely applied to daily life of people, such as mobile rechargeable equipment, portable computers, mobile phones, electric automobiles and the like. However, it seems not practical to apply it to energy storage systems on a large scale because the total abundance of available lithium ore resources on earth is low and the distribution is extremely unbalanced, and the price is easily manipulated by some political factors. Therefore, it is a good choice to develop alternative metal-ion batteries. In addition, the conventional lithium ion battery adopts a combustible organic solvent as an electrolyte, so that the safety accidents of the battery are frequent, and the wider application of the battery is seriously influenced. For this reason, safe ion batteries must also become the focus of development and application of next-generation batteries.
In the development of numerous metal-ion batteries, such as Li, Na, K, Mg, Al, Zn, Ca, etc., potassium-ion batteries have a similar mechanism and a similar electrode potential to lithium, andits natural abundance is expected to reduce cost. But K has a large ionic radius
In the process of charging and discharging, the electrode material is easy to cause larger volume expansion, thereby causing extremely poor cycle stability of the electrode material. Meanwhile, the graphite negative electrode, which has been successfully used in the lithium ion battery, has a lower theoretical capacity (279 mA. h. g) in the potassium ion battery-1) It is apparent that it severely limits the energy density of the full cell. For this reason, development of an anode material having a higher capacity is one of the keys to successful application of the potassium ion battery. Among the many alternatives, phosphorus-based cathodes have high theoretical capacity, low voltage plateaus (0.5V vs. K/K)+) And low cost, and for this reason, development of a phosphorus-based compound as a potassium ion battery has been one of the focuses of research. However, the huge volume expansion generated during the charge and discharge process thereof seriously reduces the cycle stability thereof, thereby affecting the practical use thereof. In addition, in the conventional flammable organic system, the potassium ion battery will also face a severe safety problem, and therefore, it is also important to improve the safety of the potassium ion battery and its practical application.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a zinc phosphide material, a zinc phosphide composite material, and a preparation method and application thereof, so as to improve the cycle stability and safety of a potassium ion battery and improve the actual application prospect of the potassium ion battery.
The invention is realized by the following steps:
in a first aspect, the present invention provides a zinc phosphide material comprising zinc phosphide doped with amorphous zinc phosphate.
In a second aspect, the present invention also provides a preparation method of the zinc phosphide material, which comprises: the mixture of metallic zinc, zinc oxide and phosphorus was ball milled.
In a third aspect, the present invention also provides a zinc phosphide composite material comprising a carbon material and the above zinc phosphide material.
In a fourth aspect, the present invention also provides a preparation method of the zinc phosphide composite material, which comprises: ball milling a mixture of metallic zinc, zinc oxide, phosphorus and a carbon material; or, ball milling the mixture of the zinc phosphide material and the carbon material.
In a fifth aspect, the invention also provides an application of the zinc phosphide material or the zinc phosphide composite material in preparation of a potassium ion battery cathode material.
In a sixth aspect, the present invention further provides a potassium ion battery, which includes a negative electrode, a positive electrode, and an electrolyte, wherein an active material of the negative electrode is the zinc phosphide material or the zinc phosphide composite material;
optionally, the electrolyte uses nonflammable triethyl phosphate as a solvent, optionally, the electrolyte uses triethyl phosphate as a solvent and potassium trifluoromethanesulfonylimide as a solute, and the concentration of the electrolyte is 1-5 mol/L.
The invention has the following beneficial effects: by doping zinc phosphate in zinc phosphide, the volume expansion of active zinc phosphide in the charging and discharging process can be buffered, the utilization rate of the zinc phosphide material as a potassium ion negative electrode material is improved, and the cycling stability of the electrode material is improved. In addition, zinc oxide, metal zinc and phosphorus are used as raw materials, and oxidation-reduction reaction is carried out among the zinc oxide, the metal zinc and the phosphorus through a simple one-step ball milling process, so that amorphous zinc phosphate is formed in situ while zinc phosphide is generated through reaction. The material does not need other post-treatment, the cost of the raw material and the final product is lower, and the method is beneficial to large-scale production and use. Meanwhile, the doping proportion of the zinc phosphate can be well regulated and controlled by controlling the proportion of the raw materials. Furthermore, the carbon material is mixed and added into the zinc phosphide material to form the composite material as the active material of the negative electrode material of the potassium ion battery, so that the conductivity of the negative electrode material can be further improved, the battery performance of the electrode material can be improved, and the phenomenon of conductivity reduction caused by the existence of zinc phosphate can be compensated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a process for preparing a zinc phosphide composite material;
FIG. 2 is an XRD pattern of zinc phosphate doped zinc phosphide as described in example 1, example 2 and example 3;
FIG. 3 is an XRD pattern for zinc phosphate doped zinc phosphide composites of example 7, example 8 and example 9;
FIG. 4 is an IR spectrum of zinc phosphate doped zinc phosphide composites of example 7, example 8 and example 9;
FIG. 5 is an SEM image of zinc phosphate doped zinc phosphide composites of example 7, example 8 and example 9;
FIG. 6 is a graph of the charge and discharge cycles of zinc phosphide composites doped with zinc phosphate of examples 7, 8 and 9;
FIG. 7 is a graph of charge and discharge cycles under high rate conditions for zinc phosphate doped zinc phosphide composites of examples 7, 8 and 9.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The zinc phosphide material, the zinc phosphide composite material, the preparation method and the application thereof provided by the invention are specifically explained below.
At present, the approaches for solving the cycling stability and the potassium ion safety of the phosphorus-based negative electrode material mainly have the following aspects: 1. the dimension and the scale of the material are reduced, and the material is reduced from three dimensions to a two-dimensional film or even a one-dimensional quantum dot material, so that the volume expansion capacity and the ion transmission performance of the material are improved; 2. controlling the morphology of the material, e.g., forming nanowires, nanosheets, hollow structures, core-shell structures, etc.; 3. bulk phase or surface modification, such as bulk phase heteroatom doping, crystal structure reconstruction, surface coating, and the like. Obviously, the reduction in size increases the surface area, facilitates ion diffusion and improves the material utilization rate, while a large number of side reactions also occur, and the tap density and the volume capacity are also adversely affected. In addition, the uniform morphology has great difficulty in preparation and application of a large amount on an industrial level, and meanwhile, the cost may greatly rise, which undoubtedly increases the difficulty of practical application. Based on this, the inventors have proposed the following technical solutions through a large number of studies and practices.
Some embodiments of the present invention provide a zinc phosphide material comprising zinc phosphide doped with amorphous zinc phosphate.
The zinc phosphide material is applied to preparation of the potassium ion battery cathode material as an active material, so that the cathode material has excellent cycling stability, higher energy density and higher safety coefficient. The reason for this may be: the zinc phosphide has higher theoretical capacity, but the poor cycling stability of the zinc phosphide leads the capacity of the zinc phosphide not to be fully exerted, and the amorphous zinc phosphate is doped in the zinc phosphide material and can be used as a buffer matrix to buffer the volume expansion of the zinc phosphide in the charging and discharging processes, so that the utilization rate of an active material is improved, the cycling performance of an electrode material is improved, and the safety coefficient is also improved.
In some embodiments, the zinc phosphate is present in the zinc phosphide material in an amount of from 2% to 35% by weight. Too low a content of zinc phosphate may result in failure to achieve the intended buffering effect, and too high a content may seriously affect the conductive properties of the electrode material. The mass fraction of zinc phosphate in the zinc phosphide material can be further optimized to 10% to 30%, for example, 10%, 15%, 20%, 25%, 30% or the like.
In some embodiments, the zinc phosphide material is a mixture of particles having a particle size of 100nm to 10 μm. Further, carbon materials, adhesives and the like can be added to prepare the cathode material conveniently.
In some embodiments, the zinc phosphate is formed in situ by oxidation-reduction reaction of zinc oxide and elemental phosphorus, and the zinc phosphate is doped by in situ reaction to form the zinc phosphate, so that the zinc phosphate can be uniformly distributed in the zinc phosphide, and the performance of the material is further excellent.
Referring to fig. 1, some embodiments of the present invention also provide a method for preparing the zinc phosphide material, which comprises: the mixture of metallic zinc, zinc oxide and phosphorus was ball milled.
By adopting zinc oxide, zinc metal and simple substance phosphorus as raw materials, the raw materials have wide sources and lower cost, and relatively stable redox reaction can occur among the zinc oxide, the zinc metal and the simple substance phosphorus through a simple one-step ball milling process, so that the zinc phosphide material doped with zinc phosphate with a certain mass proportion can be obtained. The material is obtained by simple ball milling, other post-treatments are not needed, the cost of the raw materials and the final product is low, and meanwhile, the zinc phosphate doping ratio can be conveniently regulated and controlled through the raw material ratio, so that the large-scale production and use of the product are facilitated.
In order to make the reaction process more stable and the material uniformity after the reaction better, in some embodiments, the rotation speed of the ball mill may be 100rpm to 1000rpm, preferably 500rpm to 1000rpm, more preferably 600rpm to 800rpm, the ball milling time may be 1h to 48h, preferably 2h to 20h, more preferably 4h to 10h, and the ball-to-material ratio is (10 to 60):1, preferably (20 to 50):1, more preferably (20 to 40): 1. For example, the ball milling speed can be 800rpm, the ball milling time can be 4h, and the ball-to-material ratio can be 40: 1.
Further, in order to prevent the phosphorus from burning during the reaction and to generate additional impurities, the whole ball milling is performed under an inert atmosphere, for example, under an argon atmosphere, but may be performed under an atmosphere of other noble gas or nitrogen which does not react with the raw material.
In order to allow the reaction between the raw materials to proceed better and facilitate ball milling, in some embodiments of the present invention, the raw materials are required to have a size, for example, the metallic zinc has an average particle size of 500nm to 5000 μm, preferably 500nm to 100 μm, and more preferably 1 μm to 10 μm. The zinc oxide has an average particle diameter of 10nm to 1000. mu.m, more preferably 500nm to 100. mu.m, and most preferably 1 to 10 μm. The average particle size of the elemental phosphorus is 5nm to 5000 μm, more preferably 100nm to 100 μm, and most preferably 500n to 10 μm.
Further, in some embodiments, the phosphorus includes, but is not limited to, one or more of red phosphorus, black phosphorus, yellow phosphorus, purple phosphorus, and white phosphorus. Meanwhile, the dimension of the phosphorus can be 0-3.
Some embodiments of the present invention also provide a zinc phosphide composite material comprising a carbon material and the above-described zinc phosphide material. The carbon material acts as a conductive agent, and is added to the material, so that the problem of conductivity reduction caused by the presence of zinc phosphate can be improved, and the battery performance of the electrode material can be improved.
In some embodiments, the mass ratio of zinc phosphide material to the carbon material is 100: (10 to 90), more preferably 100: (10-50), most preferably 100: (10-30).
Meanwhile, in order to fully and uniformly mix the carbon material and the zinc phosphide material, the average particle size of the carbon material can be 50 nm-100 μm, more preferably 50-10 μm, and most preferably 100-1 μm.
The carbon material includes, but is not limited to, one or more of graphite, graphene, carbon nanotubes, carbon nanofibers, carbon nanodots, carbon nanocones, coke, activated carbon, conductive carbon black, and acetylene black. When the carbon material is two or more of the above specific choices, the embodiment of the present invention does not have any particular limitation on the ratio of the specific materials, and the specific materials may be mixed at any ratio.
Some embodiments of the present invention also provide a method for preparing the zinc phosphide composite material, which comprises:
ball milling a mixture of metallic zinc, zinc oxide, phosphorus and a carbon material;
or, a mixture of zinc phosphide material and carbon material is ball milled.
The limitation of the types and the amounts of the metal zinc, the zinc oxide and the phosphorus refers to the relevant content of the preparation of the zinc phosphide material, and the selection of the types and the amounts of the carbon materials refers to the selection of the zinc phosphide composite material, which is not described herein again.
Some embodiments of the invention also provide application of the zinc phosphide material or the zinc phosphide composite material in preparation of a potassium ion battery negative electrode material. In the embodiment of the present invention, the zinc phosphide composite material is preferable as the negative electrode material of the potassium ion battery; the method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
Some embodiments of the present invention also provide a potassium ion battery including a negative electrode, a positive electrode, and an electrolyte, wherein an active material of the negative electrode is the above-described zinc phosphide material or the above-described zinc phosphide composite material.
In some embodiments, the electrolyte is a non-flammable triethyl phosphate solvent, optionally, the electrolyte is a triethyl phosphate solvent, potassium trifluoromethanesulfonyl imide is a solute, and the concentration of the electrolyte is 1-5 mol/L.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a zinc phosphide material, which comprises the following specific steps:
zn metal (2.2g) having an average particle size of 20 μm, ZnO (1.0g) having an average particle size of 200 nm, and red phosphorus (2.7g) having an average particle size of 20 μm were mixed and ball-milled under an argon atmosphere at a ball-to-feed ratio of 40:1, the rotating speed is 800rpm, the time is 4 hours, and the zinc phosphate doped zinc phosphide material with the mass fraction of 10 wt% is obtained.
Example 2
The embodiment provides a preparation method of a zinc phosphide material, which comprises the following specific steps:
zn metal (0.7g) having an average particle size of 20 μm, ZnO (1.0g) having an average particle size of 200 nm and red phosphorus (1.2g) having an average particle size of 20 μm were mixed and ball-milled under an argon atmosphere at a ball-to-feed ratio of 40:1, the rotating speed is 800rpm, and the time is 4 hours, so that the zinc phosphate doped zinc phosphide material with the mass fraction of 20 wt% is obtained.
Example 3
The embodiment provides a preparation method of a zinc phosphide material, which comprises the following specific steps:
zn metal (0.21g) having an average particle size of 20 μm, ZnO (1.0g) having an average particle size of 200 nm and red phosphorus (0.77g) having an average particle size of 20 μm were mixed and ball-milled under an argon atmosphere at a ball-to-feed ratio of 40:1, the rotating speed is 800rpm, the time is 4 hours, and the zinc phosphate doped zinc phosphide material with the mass fraction of 30 wt% is obtained.
Example 4
The embodiment provides a preparation method of a zinc phosphide material, which comprises the following specific steps:
zn metal (0.21g) having an average particle size of 10 μm, ZnO (1.0g) having an average particle size of 1 μm and red phosphorus (0.77g) having an average particle size of 10 μm were mixed and ball-milled under an argon atmosphere at a ball-to-feed ratio of 50: 1, the rotating speed is 300rpm, and the time is 6h, so that the zinc phosphate doped zinc phosphide material with the mass fraction of 30 wt% is obtained.
Example 5
The embodiment provides a preparation method of a zinc phosphide material, which comprises the following specific steps:
zn metal (0.7g) having an average particle size of 700 nm, ZnO (1.0g) having an average particle size of 20 μm and red phosphorus (1.2g) having an average particle size of 800 nm were mixed and ball-milled under an argon atmosphere at a ball-to-material ratio of 20: 1, the rotating speed is 1000rpm, and the time is 8 hours, so that the zinc phosphate doped zinc phosphide material with the mass fraction of 20 wt% is obtained.
Example 6
The embodiment provides a preparation method of a zinc phosphide material, which comprises the following specific steps:
zn metal (0.7g) having an average particle size of 100 μm, ZnO (1.0g) having an average particle size of 100nm, and red phosphorus (1.2g) having an average particle size of 800 nm were mixed and ball-milled under an argon atmosphere at a ball-to-feed ratio of 60: 1, the rotating speed is 600rpm, and the time is 3 hours, so that the zinc phosphate doped zinc phosphide material with the mass fraction of 20 wt% is obtained.
Example 7
The embodiment provides a preparation method of a zinc phosphide composite material, which comprises the following specific steps:
zn metal (2.2g) having an average particle size of 20 μm, ZnO (1.0g) having an average particle size of 200 nm, red phosphorus (2.7g) having an average particle size of 20 μm and a carbon material (2.5g) having an average particle size of 500nm were mixed and ball-milled in an argon atmosphere at a ball-to-material ratio of 40:1, the rotating speed is 800rpm, and the time is 4 hours, so that the zinc phosphide composite material is obtained.
Example 8
The embodiment provides a preparation method of a zinc phosphide composite material, which comprises the following specific steps:
zn metal (0.7g) having an average particle size of 20 μm, ZnO (1.0g) having an average particle size of 200 nm, red phosphorus (1.2g) having an average particle size of 20 μm, and a carbon material (1.2g) having an average particle size of 500nm were mixed and ball-milled in an argon atmosphere at a ball-to-material ratio of 40:1, the rotating speed is 800rpm, and the time is 4 hours, so that the zinc phosphide composite material is obtained.
Example 9
The embodiment provides a preparation method of a zinc phosphide composite material, which comprises the following specific steps:
zn metal (0.21g) having an average particle size of 20 μm, ZnO (1.0g) having an average particle size of 200 nm, red phosphorus (0.77g) having an average particle size of 20 μm and a carbon material (0.8g) having an average particle size of 500nm were mixed and ball-milled in an argon atmosphere at a ball-to-material ratio of 40:1, the rotating speed is 800rpm, and the time is 4 hours, so that the zinc phosphide composite material is obtained.
Test examples
XRD test was carried out on the zinc phosphate-doped zinc phosphide materials obtained in examples 1 to 3, and the test results are shown in FIG. 2. As can be seen from FIG. 2, in all of examples 1 to 3, metal phosphide was successfully synthesized, and the metal phosphide was ZnP2However, since zinc phosphate is amorphous, XRD does not show any significant effect.
XRD (X-ray diffraction) tests of the zinc phosphide composite materials obtained in the examples 7-9 show that the XRD test results are shown in figure 3, and as can be seen from figure 3, the metal phosphide is successfully synthesized in the examples 7-9, and is ZnP2However, since zinc phosphate is amorphousXRD did not show any evidence. Further, in order to verify the presence of zinc phosphate, the zinc phosphate composites prepared in examples 7 to 9 were subjected to infrared spectroscopic tests, and the results of the tests are shown in FIG. 4, in which a significant phosphate absorption peak was present. And all samples were composed of irregular particles ranging from several tens of nanometers to several tens of micrometers (fig. 5).
The zinc phosphate composite materials with different zinc phosphate contents prepared in examples 7-9 are used as active materials, acetylene black is used as a conductive agent, CMC (sodium carboxymethylcellulose) and SBR (styrene butadiene rubber) are used as binders, and the mass ratio of the CMC to the SBR is 1: 1. the mass ratio of the active material to the conductive agent to the binder is 7:1.5: 1.5; the copper foil is used as a current collector, potassium metal is used as a counter electrode, electrolyte is KFSI (potassium trifluoromethanesulfonylimide) -TEP with the concentration of 2.0mol/L, a half-cell is assembled, and the half-cell is subjected to a cycle stability test under the following test conditions: constant current charge and discharge, voltage interval: 0.01-3.0V, and 650 cycles after different multiplying power tests. As shown in FIG. 6, when the zinc phosphide composite material containing 20% zinc phosphate obtained in example 8 was used in a potassium ion battery test, the material exhibited a high specific capacity (at 0.1A g) in an electrolyte of non-combustible triethyl phosphate (TEP)-1Under the condition of current density, the capacity can reach 571.1mA h g-1) And as can be seen from FIG. 7, is at 0.5A g-1Under the condition of current density, after 1000 cycles, the residual reversible capacity is 484.9mA h g-1Capacity retention rate 94.5%).
In summary, in the embodiments of the present invention, zinc phosphate is doped into zinc phosphide, which can buffer the volume expansion of active zinc phosphide during charging and discharging, improve the utilization rate of the zinc phosphide material as a potassium ion negative electrode material, and improve the cycling stability of the electrode material. In addition, zinc oxide, metal zinc and phosphorus are used as raw materials, and oxidation-reduction reaction is carried out among the zinc oxide, the metal zinc and the phosphorus through a simple one-step ball milling process, so that amorphous zinc phosphate is formed in situ while zinc phosphide is generated through reaction. The material does not need other post-treatment, the cost of the raw material and the final product is lower, and the method is beneficial to large-scale production and use. Meanwhile, the doping proportion of the zinc phosphate can be well regulated and controlled by controlling the proportion of the raw materials. Furthermore, the carbon material is mixed and added into the zinc phosphide material to form the composite material as the active material of the negative electrode material of the potassium ion battery, so that the conductivity of the negative electrode material can be further improved, the battery performance of the electrode material can be improved, and the phenomenon of conductivity reduction caused by the existence of zinc phosphate can be compensated.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A zinc phosphide material is characterized by comprising zinc phosphide, wherein amorphous zinc phosphate is doped in the zinc phosphide.
2. The zinc phosphide material according to claim 1, wherein the mass fraction of the zinc phosphate in the zinc phosphide material is 2% to 35%, preferably 10% to 30%, more preferably 20%;
preferably, the zinc phosphide material is a particle mixture with the particle size of 100 nm-10 mu m;
preferably, the zinc phosphate is formed in situ by oxidation-reduction reaction of zinc oxide and elemental phosphorus.
3. A method of producing a zinc phosphide material as set forth in claim 1 or 2, characterized by comprising: the mixture of metallic zinc, zinc oxide and phosphorus was ball milled.
4. The preparation method of the zinc phosphide material, according to the claim 3, is characterized in that the rotation speed of the ball milling is 100-1000 rpm, preferably 500-1000 rpm, more preferably 600-800 rpm, the ball milling time is 1-48 h, preferably 2-20 h, more preferably 4-10 h, the ball-to-material ratio is (10-60): 1, preferably (20-50): 1, more preferably (20-40): 1;
preferably, the ball milling is performed under an inert atmosphere, more preferably, the ball milling is performed under an argon atmosphere.
5. The method for producing a zinc phosphide material according to claim 3, wherein the metal zinc has an average particle diameter of 500nm to 5000 μm, preferably 500nm to 100 μm, more preferably 1 μm to 10 μm;
preferably, the zinc oxide has an average particle size of 10nm to 1000 μm, more preferably 500nm to 100 μm, most preferably 1 μm to 10 μm;
preferably, the phosphorus comprises one or more of red phosphorus, black phosphorus, yellow phosphorus, purple phosphorus and white phosphorus, preferably, the dimension of the phosphorus is 0-3 dimensions, preferably, the average particle size of the phosphorus is 5 nm-5000 microns, more preferably 100 nm-100 microns, and most preferably 500 nm-10 microns.
6. A zinc phosphide composite material comprising a carbon material and the zinc phosphide material as set forth in claim 1 or 2.
7. The zinc phosphide composite material according to claim 6, wherein the mass ratio of the zinc phosphide material to the carbon material is 100: (10 to 90), more preferably 100: (10-50), most preferably 100: (10-30);
preferably, the carbon material has an average particle diameter of 50nm to 100 μm, more preferably 50 to 10 μm, and most preferably 100 to 1 μm;
preferably, the carbon material includes one or more of graphite, graphene, carbon nanotubes, carbon nanofibers, carbon nanodots, carbon nanocones, coke, activated carbon, conductive carbon black, and acetylene black.
8. A process for the preparation of a zinc phosphide composite material as claimed in claim 6 or 7, which comprises:
ball milling a mixture of metallic zinc, zinc oxide, phosphorus and a carbon material;
or, ball milling the mixture of the zinc phosphide material and the carbon material.
9. Use of a zinc phosphide material as defined in claim 1 or 2 or a zinc phosphide composite material as defined in claim 6 or 7 in the preparation of a potassium ion battery negative electrode material.
10. A potassium ion battery, characterized in that it comprises a negative electrode, a positive electrode and an electrolyte, the active material of the negative electrode is the zinc phosphide material as defined in claim 1 or 2 or the zinc phosphide composite material as defined in claim 6 or 7;
preferably, the electrolyte uses nonflammable triethyl phosphate as a solvent, and more preferably, the electrolyte uses triethyl phosphate as a solvent and potassium trifluoromethanesulfonylimide as a solute, and the concentration of the electrolyte is 1-5 mol/L.
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