CN117810385A - Zinc phosphide/zinc phosphate composite material and preparation method and application thereof - Google Patents
Zinc phosphide/zinc phosphate composite material and preparation method and application thereof Download PDFInfo
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- CN117810385A CN117810385A CN202311640213.6A CN202311640213A CN117810385A CN 117810385 A CN117810385 A CN 117810385A CN 202311640213 A CN202311640213 A CN 202311640213A CN 117810385 A CN117810385 A CN 117810385A
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- 239000006011 Zinc phosphide Substances 0.000 title claims abstract description 86
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229940048462 zinc phosphide Drugs 0.000 title claims abstract description 86
- 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 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 71
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000498 ball milling Methods 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 50
- 239000011787 zinc oxide Substances 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 2
- 238000009396 hybridization Methods 0.000 claims description 2
- 239000002110 nanocone Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 17
- 238000007599 discharging Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 27
- 229910001416 lithium ion Inorganic materials 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 22
- 239000011148 porous material Substances 0.000 description 14
- 229910021383 artificial graphite Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 238000000713 high-energy ball milling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical class [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance 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
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a zinc phosphide/zinc phosphate composite material, and a preparation method and application thereof. The zinc phosphide/zinc phosphate composite material comprises zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material thereof; and zinc phosphide is coated with zinc phosphate, carbon-based material or hybrid material of carbon-based material. The amorphous zinc phosphate is utilized, so that the volume expansion of the battery in the charging and discharging process can be effectively slowed down, and the cycle performance of the material is improved; in addition, the carbon-based material or the hybrid material of the carbon-based material is coated with zinc phosphide, so that the conductivity of the material can be improved, the rate performance can be improved, the problem of conductivity reduction caused by the existence of zinc phosphate can be solved, and the battery has good rate performance and cycle stability. Meanwhile, the coating of the carbon-based material or the hybrid material thereof can reduce the generation of white phosphorus during ball milling, improve the thermal stability of the material, promote the covalent bond connection of phosphorus and carbon during ball milling, and improve the electrochemical performance while stabilizing the structure.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a zinc phosphide/zinc phosphate composite material, and a preparation method and application thereof.
Background
Along with the increasing demand of high-energy-density energy storage equipment, lithium ion batteries become the most widely used portable storage equipment at present due to the advantages of long cycle life, high energy density, good multiplying power performance and the like. One of the key challenges in designing fast charge lithium ion batteries is to build high rate and excellent safety anode materials. The negative electrode materials of the lithium ion battery mainly comprise three kinds of graphite (theoretical specific capacity 372 mAh/g), but the capacity of natural graphite and artificial graphite is hardly improved because the capacity of the natural graphite and the artificial graphite is applied to the basic theoretical limit value of raw materials. Secondly, both the conductivity and the capacity of the nanostructured carbon based materials and metal oxides are low and the performance is poor. For the silicon-carbon anode material, various lithium silicon compounds are formed in the silicon-lithium alloying process, the phase change is complex, the volume change in the charging and discharging process is large, and the stability is poor. Finally, for the phosphorus-based negative electrode material, the natural reserve resources of phosphorus are rich, the price is low, and the theoretical specific capacity is as high as 2596mAh/g (Li 3 P), lower voltage plateau (Li/Li) + 0.8V), phosphorus and silicon are both alloyed cathodes, but the lithium intercalation potential is high, and lithium precipitation potential is difficult to reach even if polarization occurs at high magnification. However, the disadvantages of the phosphorus-based anode material are obvious, such as poor conductivity, high expansion rate and the like, which lead to poor cycling stability of the electrode material in the charge and discharge processes, thereby greatly limiting the application of the phosphorus-based anode material in metal ion batteries.
Therefore, it is needed to provide a composite material, which can effectively relieve the volume expansion of the battery during the charge and discharge process, and improve the cycle performance, conductivity and rate performance of the material, so that the prepared battery has good rate performance and cycle stability.
Disclosure of Invention
The present invention is directed to solving one or more of the problems of the prior art and providing at least one of a beneficial choice or creation of conditions. The invention provides a zinc phosphide/zinc phosphate composite material which can effectively relieve the volume expansion of a battery in the charge and discharge process, improve the cycle performance, conductivity and rate capability of the material, and ensure that the prepared battery has good rate capability and cycle stability.
The invention is characterized in that: the composite material comprises zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material of the carbon-based material; and the zinc phosphide is coated with the zinc phosphate, the carbon-based material or a hybrid material of a carbon-based material. The existence of the zinc phosphate can effectively relieve the volume expansion of the zinc phosphide composite material in the charging and discharging processes, avoid the falling-off phenomenon of the composite material caused by the volume expansion, improve the cycle performance of the material and play a role of SEI film to a certain extent; in addition, the carbon-based material or the hybrid material thereof is coated with zinc phosphide, so that the conductivity of the material can be improved, the rate capability of the material can be improved, the problem of conductivity reduction caused by the existence of zinc phosphate can be solved, and the prepared battery has good rate capability and cycle stability. Meanwhile, the generation of white phosphorus in the ball milling process can be reduced by coating the carbon-based material or the hybrid material of the carbon-based material, the thermal stability of the material is improved, and the electrochemical performance of the battery is further improved.
Accordingly, in a first aspect the present invention provides a zinc phosphide/zinc phosphate composite material.
Specifically, the zinc phosphide/zinc phosphate composite material comprises zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material of a carbon-based material; and the zinc phosphide is coated with the zinc phosphate, the carbon-based material or a hybrid material of a carbon-based material.
Preferably, in the composite material, the mass ratio of the zinc phosphide, the zinc phosphate, the carbon-based material or the hybrid material of the carbon-based material is 1: (0.01-1.1): (0.01-2.2).
Further preferably, in the composite material, the mass ratio of the zinc phosphide, zinc phosphate, carbon-based material or hybrid material of the carbon-based material is 1: (0.01-1): (0.01-2).
Preferably, the carbon-based material is at least one selected from graphite, graphene, carbon nanotubes, carbon nanofibers, carbon nanodots, carbon nanocones, coke, activated carbon, conductive carbon black, and acetylene black.
Preferably, the hybrid material of the carbon-based material is obtained by introducing a hybrid element into the carbon-based material; the hybridization element comprises at least one of Li, P and N.
Preferably, the specific surface area of the composite material is 1-10m 2 /g; further preferably, the specific surface area of the composite material is 2-5m 2 /g。
Preferably, the pore diameter of the composite material is 18-130nm; further preferably, the pore size of the composite material is 20-120nm.
Preferably, the particle size of the composite material is 10nm-100 μm; further preferably, the particle size of the composite material is 100nm to 10 μm.
In a second aspect, the invention provides a method for preparing the zinc phosphide/zinc phosphate composite material according to the first aspect of the invention.
Specifically, the preparation method of the zinc phosphide/zinc phosphate composite material comprises the following steps:
mixing zinc oxide, phosphorus simple substance, carbon-based material or hybrid material of the carbon-based material to obtain a mixture, and then ball milling the mixture to obtain the composite material; or mixing zinc oxide and phosphorus simple substances to obtain a mixture, ball-milling the mixture, and then adding a carbon-based material or a hybrid material of the carbon-based material to prepare the composite material; or mixing zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material of the carbon-based material to obtain a mixture, and then ball-milling the mixture to obtain the composite material.
Specifically, particle collision and friction in the ball milling process are beneficial to particle refinement and surface modification, so that zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material of the carbon-based material is mixed and ball milled, and the zinc phosphide is coated by the zinc phosphate, the carbon-based material or the hybrid material of the carbon-based material.
Preferably, the elemental phosphorus includes at least one of Red Phosphorus (RP), white Phosphorus (WP), violet phosphorus (PP), black Phosphorus (BP), and Yellow Phosphorus (YP).
Preferably, the zinc oxide has a size of 0.9nm to 11mm; further preferably, the zinc oxide has a size of 1nm to 10mm.
Preferably, the size of the elemental phosphorus is 0.9nm to 110mm, and further preferably, the size of the elemental phosphorus is 1nm to 100mm.
Preferably, the elemental phosphorus has a dimension of 0 to 3 dimensions.
Preferably, the carbon-based material or the hybrid material of the carbon-based material accounts for 3-99% of the total mass of the zinc oxide, the elemental phosphorus, the carbon-based material or the hybrid material of the carbon-based material.
Further preferably, the carbon-based material or the hybrid material of the carbon-based material accounts for 20-60% of the total mass of the zinc oxide, the elemental phosphorus, the carbon-based material or the hybrid material of the carbon-based material.
Preferably, the molar ratio of the zinc oxide to the phosphorus element is 0.1-20:1.
further preferably, the molar ratio of the zinc oxide to the phosphorus element is 0.3 to 3:1.
preferably, the mass ratio of ball grinding balls to the mixture used in the ball milling is 18-110:1.
further preferably, the mass ratio of the ball grinding balls to the mixture used in the ball milling is 20-100:1.
still more preferably, the mass ratio of ball grinding balls and mixture used in the ball milling is 40:1.
preferably, the rotation speed of the ball milling is 200-1500rpm; the ball milling time is 9.5-100h.
Further preferably, the rotational speed of the ball mill is 800-1000rpm; the ball milling time is 10-96h.
Preferably, the ball milling is performed in an inert atmosphere, which is an argon atmosphere.
Specifically, the ball milling can promote the covalent bond connection of phosphorus and carbon, promote the conduction capacity of lithium ions in the material while stabilizing the structure, enhance the conductivity of the composite material and help to obtain stable and excellent electrochemical performance.
A third aspect of the present invention provides a negative electrode material.
Specifically, the negative electrode material comprises the zinc phosphide/zinc phosphate composite material according to the first aspect of the present invention.
Preferably, the negative electrode material further comprises a conductive agent and a binder.
Preferably, the mass ratio of the zinc phosphide/zinc phosphate composite material, the conductive agent and the binder is 7: (0.04-110): (0.04-33).
Further preferably, the mass ratio of the zinc phosphide/zinc phosphate composite material, the conductive agent and the binder is 7: (0.05-100): (0.05-30).
Preferably, the conductive agent includes at least one of conductive carbon black (Super P), acetylene Black (AB), ketjen Black (KB), vapor Grown Carbon Fiber (VGCF), carbon Nanotube (CNT), conductive graphite, graphene.
Further preferably, the conductive agent is acetylene black.
Preferably, the binder includes at least one of polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), styrene Butadiene Rubber (SBR).
Further preferably, the binder includes at least one of CMC and SBR.
The fourth aspect of the present invention also provides a negative electrode tab.
Specifically, the negative electrode plate comprises a coating formed by the negative electrode material according to the third aspect of the invention.
Preferably, the preparation method of the negative electrode plate comprises the following steps:
(1) Mixing the zinc phosphide/zinc phosphate composite material, a conductive agent and a binder to obtain slurry;
(2) And coating the slurry on the surface of the metal foil, and drying to obtain the negative electrode plate.
Preferably, in step (2), the metal foil is copper foil.
Preferably, in step (2), the drying is vacuum drying; the temperature of the vacuum drying is 45-130 ℃; the time of vacuum drying is 1.5-40h.
Further preferably, the temperature of the vacuum drying is 50-120 ℃; the time of vacuum drying is 2-36h.
The fifth aspect of the invention also provides a battery.
Specifically, the battery comprises the negative electrode plate according to the fourth aspect of the invention.
Preferably, the battery is a lithium ion battery.
Preferably, the lithium ion battery is a lithium ion battery half-cell.
Preferably, the preparation method of the lithium ion battery half-cell comprises the following steps:
and stacking and placing the negative electrode plate, the diaphragm, the metal lithium sheet, the gasket and the elastic sheet in the battery shell from top to bottom, then dripping electrolyte into the battery shell, covering the battery shell, sealing, and standing to obtain the lithium ion battery half-cell.
Preferably, the pressure of the seal is 18-110MPa; further preferably, the pressure of the seal is 20-100MPa.
Preferably, the standing time is 9-80h; further preferably, the time of the standing is 10 to 72 hours.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The composite material comprises zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material of the carbon-based material; and the zinc phosphide is coated with the zinc phosphate, carbon-based material or hybrid material of carbon-based material. The existence of the zinc phosphate can effectively relieve the volume expansion of the zinc phosphide composite material in the charging and discharging processes, avoid the falling-off phenomenon of the composite material caused by the volume expansion, improve the cycle performance of the material and play a role of SEI film to a certain extent; in addition, the carbon-based material or the hybrid material thereof is coated with zinc phosphide, so that the conductivity of the material can be improved, the rate capability of the material can be improved, the problem of conductivity reduction caused by the existence of zinc phosphate can be solved, and the prepared battery has good rate capability and cycle stability. Meanwhile, the generation of white phosphorus in the ball milling process can be reduced by coating the carbon-based material or the hybrid material of the carbon-based material, the thermal stability of the material is improved, and the electrochemical performance of the battery is further improved.
(2) The increase of the content of the carbon-based material or the hybrid material of the carbon-based material is beneficial to improving the conductivity of a material system, improving the fineness of powder after ball milling, improving the compact agglomeration of zinc phosphide particles, simultaneously being beneficial to converting zinc phosphide from a crystalline state to an amorphous state structure, increasing more abundant porous structures and holes, improving the lithium storage capacity and further improving the electrochemical performance of a battery.
(3) The composite material has nanometer pores on the surface, which is favorable for improving the diffusion and permeation of electrolyte and can be Li + Providing more inlets to reduce Li during charge and discharge + And the diffusion resistance of the lithium ion battery is improved, and the rate performance and the cycle stability of the quick-charge lithium ion battery are improved. In addition, the composite system of the invention has reversible Li + The storage mechanism is beneficial to reducing the structural stress in the cycling process, and can relieve the volume expansion in the electrode charging and discharging process, so that the battery has good cycling stability.
(4) The preparation method is simple in preparation process, can realize the large-scale production of the composite material by adopting a simple and efficient high-energy ball milling mode, has high production efficiency and low cost, and is convenient for industrial production. In addition, the amorphous zinc phosphate is generated in situ while zinc phosphide is generated by adopting a ball milling method, so that the volume expansion of the zinc phosphide composite material in the charge and discharge process can be effectively relieved by the existence of the zinc phosphate, the falling-off phenomenon of the composite material caused by the volume expansion is avoided, and the cycle performance of the material is improved. Meanwhile, the high-energy ball milling also promotes the covalent bond connection of phosphorus and carbon, improves the conduction capacity of the material to lithium ions while stabilizing the structure, enhances the conductivity of the composite material, and is favorable for obtaining stable and excellent electrochemical performance.
Drawings
FIG. 1 is an SEM image of a zinc phosphide/zinc phosphate composite material of examples 1-3, a material of comparative example 1;
FIG. 2 is a graph showing the desorption of nitrogen from the zinc phosphide/zinc phosphate composite materials of examples 1-3 and the material of comparative example 1 according to the present invention;
FIG. 3 is a graph showing pore size distribution of the zinc phosphide/zinc phosphate composite materials of examples 1-3 and the material of comparative example 1 according to the present invention;
FIG. 4 is an EDS spectrum of zinc phosphide/zinc phosphate composite materials according to examples 1-3 of the present invention;
FIG. 5 is an XRD diffraction pattern of zinc phosphide/zinc phosphate composites according to examples 1-3 of the present invention;
FIG. 6 is a FTIR graph of zinc phosphide/zinc phosphate composites according to examples 1-3 of the present invention;
FIG. 7 is a TEM image of the zinc phosphide/zinc phosphate composite material of example 1 of the present invention;
FIG. 8 is a graph showing the rate performance of half batteries of lithium ion batteries of application examples 1 to 3 and comparative application example 1 at 0.1 to 5A/g;
FIG. 9 is a graph showing the rate performance of half batteries of lithium ion batteries of application examples 1-3 of the present invention at 0.1-10A/g;
FIG. 10 is a graph showing the rate performance of a half cell of the lithium ion battery of application example 3 of the present invention at 0.05-25A/g;
FIG. 11 is a graph showing the long cycle performance at 5A/g of half-cells of lithium ion batteries of application examples 1-3 of the present invention;
fig. 12 is a graph showing the long cycle performance at 15A/g of a half cell of a lithium ion battery according to application example 3 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The embodiment of the invention adopts nano ZnO particles and millimeter red phosphorus as raw materials, wherein the average particle diameter D50 of ZnO in the embodiment 1 is 100nm, and the average particle diameter D50 of red phosphorus is 2mm. The average particle diameter D50 of ZnO in example 2 was 200nm, and the average particle diameter D50 of red phosphorus was 5mm. The average particle diameter D50 of ZnO in example 3 was 100nm, and the average particle diameter D50 of red phosphorus was 5mm.
In the performance test of the embodiment of the invention, the specific capacity of the negative electrode is calculated by taking the weight of the active substances of zinc phosphide and zinc phosphate as the reference, and the mass of the conductive carbon black is not contained.
Example 1
A zinc phosphide/zinc phosphate composite material comprises zinc phosphide, zinc phosphate and conductive carbon black; the zinc phosphide is coated with zinc phosphate and conductive carbon black.
A preparation method of a zinc phosphide/zinc phosphate composite material comprises the following steps:
0.53g ZnO, 0.40g red phosphorus and 0.28g conductive carbon black (Super P) are weighed, the Super P accounts for 23 percent of the total weight of ZnO, red phosphorus and Super P, and the materials are placed in a ball milling tank, and the ball-material ratio is 40:1, under the argon atmosphere, the ball milling speed is 800rpm, the ball milling time is 4.5 hours, and the zinc phosphide/zinc phosphate composite material c-ZnP is prepared 2 /Zn 3 (PO 4 ) 2 /C23。
Example 2
A zinc phosphide/zinc phosphate composite material comprises zinc phosphide, zinc phosphate and conductive carbon black; the zinc phosphide is coated with zinc phosphate and conductive carbon black.
A preparation method of a zinc phosphide/zinc phosphate composite material comprises the following steps:
1.10g ZnO, 0.84g red phosphorus and 0.83g Super P,Super P accounting for 30 percent of the total weight of ZnO, red phosphorus and Super P are weighed, placed in a ball milling tank, and have a ball-to-material ratio of 40:1, ball milling is carried out for 4 hours at the speed of 850rpm under the argon atmosphere, so as to obtain the zinc phosphide/zinc phosphate composite material c-ZnP 2 /Zn 3 (PO 4 ) 2 /C30。
Example 3
A zinc phosphide/zinc phosphate composite material comprises zinc phosphide, zinc phosphate and conductive carbon black; the zinc phosphide is coated with zinc phosphate and conductive carbon black.
A preparation method of a zinc phosphide/zinc phosphate composite material comprises the following steps:
0.98g ZnO, 0.75g red phosphorus and 0.97g Super P,Super P accounting for 36 percent of the total weight of ZnO, red phosphorus and Super P are weighed, placed in a ball milling tank, and the ball-to-material ratio is 40:1, ball milling is carried out for 4.5 hours at the speed of 850rpm under the argon atmosphere, so as to obtain the zinc phosphide/zinc phosphate composite material a-ZnP 2 /Zn 3 (PO 4 ) 2 /C36。
Comparative example 1
Commercially available artificial graphite was used as the material of comparative example 1.
Application example 1
The zinc phosphide/zinc phosphate composite material prepared in example 1 was used as an active material.
The preparation method of the lithium ion battery half-cell comprises the following steps:
(1) Mixing a zinc phosphide/zinc phosphate composite material, a binder CMC and SBR (mass ratio=1:1) and a conductive agent acetylene black according to a mass ratio of 7:1.5:1.5 to obtain slurry;
(2) Uniformly coating the slurry obtained in the step (1) on a Cu foil current collector, and vacuum drying for 16 hours at the temperature of 60 ℃ to obtain a negative electrode plate;
(3) Stacking the negative electrode plate, the diaphragm, the metal lithium plate, the gasket and the spring piece obtained in the step (2) in the sequence from top to bottom in an argon atmosphere glove box, placing the stacked materials in a battery shell, and then dripping 1.0M LiPF (lithium ion battery) electrolyte into the battery shell 6 (the solvent is ethylene carbonate/diethyl carbonate (EC/DEC), the volume ratio is 1:1; the additive is 10wt% fluoroethylene carbonate (FEC) and 1wt% Vinylene Carbonate (VC)), the battery shell is covered, the battery shell stays at the pressure of 50MPa for sealing, and finally the battery shell is placed at normal temperature for 24 hours to obtain the half battery of the lithium ion battery.
Application example 2
Application example 2 differs from application example 1 only in that application example 2 uses the zinc phosphide/zinc phosphate composite material prepared in example 2 as an active material, and otherwise is the same as application example 1.
Application example 3
Application example 3 differs from application example 1 only in that application example 3 uses the zinc phosphide/zinc phosphate composite material prepared in example 3 as an active material, and otherwise is the same as application example 1.
Comparative application example 1
Comparative application example 1 differs from application example 1 only in that comparative application example 1 uses the material of comparative example 1 as an active material, and otherwise is the same as application example 1.
Performance testing
Sem test
SEM morphology observations of the zinc phosphide/zinc phosphate composites prepared in examples 1-3 and the material of comparative example 1 are shown in FIG. 1. Wherein, fig. 1 (a) is an SEM image of the material of comparative example 1, artificial graphite represents artificial graphite; FIGS. 1 (B), 1 (C) and 1 (D) are SEM images of zinc phosphide/zinc phosphate composites prepared in examples 1-3, respectively. As can be seen from FIG. 1, the composite materials of examples 1-3 of the present invention have smaller and more uniform particle sizes, ranging from tens of nanometers to several micrometers, while the graphite material of comparative example 1 has larger and more uniform particle sizes.
2. Nitrogen adsorption and desorption test
The zinc phosphide/zinc phosphate composite materials prepared in examples 1 to 3 and the material of comparative example 1 were subjected to a nitrogen adsorption and desorption test by a nitrogen adsorption and desorption (BET) method, the nitrogen adsorption and desorption curves being shown in fig. 2, wherein Artificial graphite represents the artificial graphite of comparative example 1; the abscissa Relative Pressure (P/P0) represents the relative pressure of nitrogen, P0 represents the saturation vapor pressure of the gas at the adsorption temperature, and P represents the pressure of the gas phase at the adsorption equilibrium; ordinate Quantity adsorbed (cm) 3 The amount of adsorption (STP is standard) is shown in STP/g. The Pore size distribution curves are shown in FIG. 3, wherein the graph (a) and (d) in FIG. 3 respectively show the Pore size distribution curves of the artificial graphite material of comparative example 1, the Pore size distribution curves of the zinc phosphide/zinc phosphate composite materials of example 1, example 2 and example 3, and the abscissa Pore Width/nm represents the Pore size distribution (nm) and the ordinate dV/dlog (W) Pore Volume (cm) 3 /g) represents the pore area.
As can be seen from FIG. 2, the specific surface areas of the zinc phosphide/zinc phosphate composites of examples 1-3 of the present invention were 2.89m, respectively 2 /g、3.78m 2 /g、5.11m 2 Per gram, the specific surface area of the artificial graphite material of comparative example 1 was 2.43m 2 And/g. The specific surface area of the zinc phosphide/zinc phosphate composite material prepared by the method is larger than that of the artificial graphite of comparative example 1, and the specific surface area of the zinc phosphide/zinc phosphate composite material of examples 1-3 of the invention is gradually increased along with the gradual increase of the addition amount of the conductive carbon black in the carbon-based material.
As can be seen from FIG. 3, the pore size distribution of the composite material of examples 1-3 of the present invention is mainly 20-100nm, the pore size distribution of the artificial graphite material of comparative example 1 is mainly 10-120nm, and the nano-pores of the present invention are favorable for improving the diffusion and permeation of electrolyte, and can also be Li + Providing more inlets to reduce Li during charge and discharge + And the diffusion resistance of the lithium ion battery is improved, and the rate performance and the cycle stability of the quick-charge lithium ion battery are improved.
EDS spectroscopy
EDS (electron discharge spectroscopy) analysis is carried out on the zinc phosphide/zinc phosphate composite materials prepared in examples 1-3 by using an energy spectrometer equipped with a scanning electron microscope, and the results are shown in FIG. 4. Wherein, the A, B and C in FIG. 4 show EDS spectra of the zinc phosphide/zinc phosphate composite materials of examples 1-3, respectively. As can be seen from fig. 4, the Zn, P, O, C elements are uniformly dispersed in the particulate material.
XRD diffraction analysis
XRD diffraction analysis was performed on the zinc phosphide/zinc phosphate composite materials prepared in examples 1 to 3, and the XRD diffraction patterns are shown in FIG. 5. Wherein the abscissa 2Theta (deg.) represents the diffraction angle 2θ (°), and the ordinate intersystem represents the diffraction intensity.
As can be seen from FIG. 5, the zinc phosphide obtained by ball milling ZnO and red phosphorus in a molar ratio of 1:2 with 23wt% of conductive carbon black in example 1 was crystalline, showing tetragonal system ZnP 2 The obvious diffraction peaks (PDF#72-1626), such as (104), (112) and (114), the space group is P4 1 2 1 2, lattice parameter isThe zinc phosphide obtained by high energy ball milling of ZnO and red phosphorus in a molar ratio of 1:2 with 30wt% of conductive carbon black in example 2 wasAmorphous state, no distinct diffraction peak. The zinc phosphide obtained by high energy ball milling of ZnO and red phosphorus in a molar ratio of 1:2 with 36wt% conductive carbon black in example 3 was amorphous with no distinct diffraction peaks. The ball milling process is beneficial to improving the conductivity of a material system along with the increase of the content of conductive carbon, improving the fineness of powder after ball milling, improving the compact agglomeration of zinc phosphide particles, simultaneously being beneficial to converting zinc phosphide from a crystalline state to an amorphous state structure, increasing more abundant porous structures and holes, improving the lithium storage capacity and further improving the electrochemical performance of a battery.
Ftir infrared analysis
FTIR infrared analysis was performed on the zinc phosphide/zinc phosphate composites prepared in examples 1-3, and FTIR graphs are shown in fig. 6. Wherein the abscissa Wavenumber (cm) -1 ) Wavelength is indicated, and absorbance is indicated on the ordinate Transmittance (a.u.).
As can be seen from fig. 6, phosphate is generated, which illustrates that examples 1-3 generate amorphous zinc phosphate in situ while ball milling to generate zinc diphosphate, and cooperatively inhibit volume expansion, so that electrochemical stability of the zinc diphosphate/zinc phosphate composite system can be improved.
TEM test
Transmission electron microscopy observation was carried out on the zinc phosphide/zinc phosphate composite material prepared in example 1, and a TEM microstructure diagram is shown in FIG. 7, wherein ZnP 2 was surrounded by amorphous super P and zinc phosphate the zinc diphosphate is coated with conductive carbon black and zinc phosphate, znP in the dashed box 2 . As can be seen from FIG. 7, in the zinc phosphide/zinc phosphate composite material of example 1, crystalline state ZnP 2 The buffer belt is distributed in the amorphous carbon-based material Super P and the coating ring of the amorphous zinc phosphate material generated in situ, provides a better buffer belt for phase change and material deformation in the charge-discharge cycle of the battery, and improves the cycle stability and the rate capability of the battery.
7. Rate capability test
The lithium ion battery half-cells prepared in application examples 1-3 and comparative application example 1 were subjected to a rate performance test, and a rate performance graph at 0.1-5A/g is shown in FIG. 8, wherein Current Density represents Current Density; artificial graphite the artificial graphite of comparative example 1; the abscissa indicates the number of cycles, and the ordinate Discharge Capacity (mAh/g) indicates the specific discharge capacity (milliamp hours per gram). The rate performance curves of the half batteries of the lithium ion batteries prepared in application examples 1-3 at 0.1-10A/g are shown in FIG. 9, wherein Current Density represents Current Density; the abscissa Cycle number represents the number of cycles, the left ordinate Discharge Capacity (mAh/g) represents the specific capacity (milliamp hour per gram), and the right ordinate Coulombic Efficiency (%) represents the coulomb efficiency (%).
As can be seen from fig. 9, the battery of application example 1 exhibited good rate performance at current densities of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A/g under the conditions of 0.01-3.0V charge-discharge interval, with specific capacities of 1243, 1150, 1061, 980, 899 and 774mA h/g, respectively. The batteries of application example 2 exhibited good rate performance at current densities of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A/g under the conditions of 0.01-3.0V charge-discharge interval, with specific capacities of 1577, 1462, 1331, 1238, 1145 and 1006m h/g, respectively. The specific capacities of the battery of application example 3 were 1669, 1546, 1407, 1299, 1193, 1121, 1069mAh/g and 800mAh/g at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, 5.0 and 10A/g, respectively, in the charge/discharge interval of 0.01 to 3.0V. And as can be seen from FIG. 9, application example 1 had a specific capacity of 619mAh/g at a high current density of 10.0A/g. Application example 2the specific capacity exceeded 800mAh/g at a high current density of 10.0A/g. Application example 3 the specific capacity was 800mAh/g at a high current density of 10.0A/g.
As can be seen from FIG. 8, the specific capacities of the batteries of comparative example 1 were 346, 286, 175, 85, 44 and 21mAh/g at current densities of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A/g, respectively, under the conditions of charge and discharge intervals of 0.01 to 3.0V, and the capacity fading was remarkable at high current densities of 5.0A/g.
The rate performance curve of the lithium ion battery half cell prepared in application example 3 at 0.05-25A/g is shown in FIG. 10, wherein activation represents activation of the battery under small Current, charge represents charging, discharge represents discharging, and Current Density represents Current Density; the abscissa Cycle number represents the number of cycles, the left ordinate Capacity (mAh/g) represents the specific Capacity (milliamp hours per gram), and the right ordinate Coulombic Efficiency (%) represents the coulomb efficiency (%). As can be seen from fig. 10, the specific capacity of the battery of application example 3 exceeded 580mAh/g at a high current density of 25.0A/g.
As can be seen from the rate performance test result, the invention can obviously improve the rate performance of the battery by utilizing in-situ generated zinc phosphide and zinc phosphate, and the amorphous structure reduces the structural stress in the circulation process and improves the electrochemical performance of the battery.
8. Long cycle performance test
The lithium ion battery half-cells prepared in application examples 1-3 were subjected to long cycle performance test at a current density of 5A/g, the long cycle performance graph being shown in FIG. 11, wherein 5A/g represents the current density and Equal to 3C represents the equivalent of 3C; the abscissa Cycle number represents the number of cycles, the left ordinate Discharge Capacity (mAh/g) represents the specific discharge capacity (milliamp hours per gram), and the right ordinate Coulombic Efficiency (%) represents the coulomb efficiency (%). As can be seen from FIG. 11, the battery of application example 1 still has a capacity of 762mAh/g after 1500 cycles under the condition of 5.0A/g and 0.01-3.0V charge-discharge interval. The battery of application example 2 still has 914mAh/g after 1500 cycles under the condition of 5.0A/g and 0.01-3.0V charge-discharge interval. The battery of application example 3 still has 1037mAh/g capacity after 1500 cycles under the condition of 5.0A/g (3C) and 0.01-3.0V charge-discharge interval, and the capacity retention rate is 97%. The battery of the invention has good cycle stability.
The battery prepared in application example 3 was subjected to a long-cycle performance test at a current density of 15A/g, and the result is shown in FIG. 12, wherein Gradient activation from 0.05.05A/g to12A/g represents the gradient activation of the test current from 0.05A/g to 12A/g; 15A/g represents the current density, and Equal to 9C represents 9C; the abscissa Cycle number represents the number of cycles, the left ordinate Discharge Capacity (mAh/g) represents the specific discharge capacity (milliamp hours per gram), and the right ordinate Coulombic Efficiency (%) represents the coulomb efficiency (%). It can be seen from FIG. 12 that the capacity is still 616mAh/g after 2500 cycles of stable cycling at a higher current density, e.g., 15.0A/g (9C), and the long cycling performance is excellent.
In conclusion, the battery prepared from the composite material has good multiplying power performance and long cycle performance. At the same time illustrate the invention ZnP 2 /Zn 3 (PO 4 ) 2 the/C system has reversible Li + The storage mechanism can relieve the capacity of volume expansion in the process of electrode charge and discharge, and has good application value in the field of fast lithium ion negative electrodes.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A composite material comprising zinc phosphide, zinc phosphate, a carbon-based material, or a hybrid material of a carbon-based material; and the zinc phosphide is coated with the zinc phosphate, the carbon-based material or a hybrid material of a carbon-based material.
2. The composite material according to claim 1, wherein the mass ratio of the zinc phosphide, zinc phosphate, carbon-based material or hybrid material of the carbon-based material in the composite material is 1: (0.01-1.1): (0.01-2.2).
3. The composite material of claim 2, wherein the carbon-based material is selected from at least one of graphite, graphene, carbon nanotubes, carbon nanofibers, carbon nanodots, carbon nanocones, coke, activated carbon, conductive carbon black, acetylene black; the hybrid material of the carbon-based material is obtained by introducing a hybrid element into the carbon-based material; the hybridization element comprises at least one of Li, P and N.
4. The composite material according to claim 1, characterized in that the specific surface area of the composite material is 1-10m 2 /g; and/or, whatThe aperture of the composite material is 18-130nm; and/or the particle size of the composite material is 10nm-100 μm.
5. A method of preparing a composite material according to any one of claims 1 to 4, comprising the steps of:
mixing zinc oxide, phosphorus simple substance, carbon-based material or hybrid material of the carbon-based material to obtain a mixture, and then ball milling the mixture to obtain the composite material; or mixing zinc oxide and phosphorus simple substances to obtain a mixture, ball-milling the mixture, and then adding a carbon-based material or a hybrid material of the carbon-based material to prepare the composite material; or mixing zinc phosphide, zinc phosphate, a carbon-based material or a hybrid material of the carbon-based material to obtain a mixture, and then ball-milling the mixture to obtain the composite material.
6. The method according to claim 5, wherein the carbon-based material or the hybrid material of the carbon-based material accounts for 3 to 99% of the total mass of the zinc oxide, the elemental phosphorus, the carbon-based material or the hybrid material of the carbon-based material; and/or the mole ratio of the zinc oxide to the phosphorus element is 0.1-20:1.
7. the method according to claim 5, wherein the ball milling is performed using a milling ball; the mass ratio of the grinding balls to the mixture is 18-110:1, a step of; and/or the rotation speed of the ball milling is 200-1500rpm; the ball milling time is 9.5-100h.
8. A negative electrode material comprising the composite material according to any one of claims 1 to 4.
9. A negative electrode sheet comprising the coating formed of the negative electrode material of claim 8.
10. A battery comprising the negative electrode tab of claim 9.
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