CN117199327B - Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof - Google Patents
Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 72
- 239000010703 silicon Substances 0.000 title claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010405 anode material Substances 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 29
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 15
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- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
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- 229910000676 Si alloy Inorganic materials 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
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- 238000000137 annealing Methods 0.000 claims description 4
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- 229910052802 copper Inorganic materials 0.000 claims description 3
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 3
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
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- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- 238000009830 intercalation Methods 0.000 claims description 3
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
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- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims 2
- 230000008859 change Effects 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract 1
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- 238000011161 development Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000006115 industrial coating Substances 0.000 description 4
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- 229910001416 lithium ion Inorganic materials 0.000 description 4
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
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- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AIOWANYIHSOXQY-UHFFFAOYSA-N cobalt silicon Chemical compound [Si].[Co] AIOWANYIHSOXQY-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910015365 Au—Si Inorganic materials 0.000 description 1
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OFLYIWITHZJFLS-UHFFFAOYSA-N [Si].[Au] Chemical compound [Si].[Au] OFLYIWITHZJFLS-UHFFFAOYSA-N 0.000 description 1
- MANBDHUBXBMZNV-UHFFFAOYSA-N [V]=[Si] Chemical compound [V]=[Si] MANBDHUBXBMZNV-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a quick-charging silicon-based anode material for a lithium battery and a preparation method thereof. The negative electrode consists of micro-nano silicon-based particles, buffer nano particle conductive channels embedded in the silicon-based particles and carbon shell conductive channels coated on the surface of the silicon-based particles. The preparation process of the negative electrode adopts a ball milling sintering process compatible with the preparation process of the industrial lithium battery material. In the charge-discharge cycle process, charges can be rapidly transferred and transmitted through a buffer nano particle conductive channel embedded in the silicon-based particles and a carbon shell layer coated on the surfaces of the silicon particles, so that the rapid charge-discharge performance of the silicon negative electrode under a large current is realized. Meanwhile, the buffer nanoparticle conductive channel embedded in the silicon-based particles and the carbon shell layer coated on the surfaces of the silicon-based particles can effectively relieve the volume change of the silicon-based anode material in the charge/discharge process, stabilize the solid electrolyte interface film (SEI) on the surfaces of the anode particles, and accordingly improve the circulation stability of the silicon-based anode material.
Description
Technical Field
The invention relates to a silicon negative electrode technology for a lithium battery, in particular to a quick-charging silicon-based negative electrode material for a lithium battery and a preparation method thereof, and belongs to the technical field of energy storage batteries.
Background
Compared with the traditional fuel vehicle, the problems of mileage anxiety, long charging time and the like become main problems for preventing the development of the electric vehicle. Therefore, the improvement of energy density and quick charge capability is a popular development goal of battery manufacturers and whole vehicle factories. Silicon is used as a negative electrode material of a lithium battery, the theoretical specific capacity of the silicon can reach 4200 mAh g-1, which is ten times of the theoretical specific capacity of a commercial graphite negative electrode, and the silicon is considered as one of the negative electrode materials with the most potential of the next-generation high-specific-energy lithium secondary battery. However, the tremendous volumetric expansion/contraction of lithium ions as they intercalate/deintercalate silicon causes the silicon particles to fracture, chalking, lose electrical contact with the substrate, greatly reducing their cycle life. The nanoscale silicon material prevents the powdering of the silicon anode material in the circulation process due to the advantages of high specific capacity, good stress release, promotion of ion/electron transmission, maintenance of structural stability and the like, and provides a solution for improving the circulation stability of the battery. Through decades of development, a high specific energy lithium battery using a silicon anode to replace a carbon anode is at the beginning of commercial application, and tens of companies at home and abroad are producing silicon anode materials with great force, so as to try to develop a next generation silicon-based lithium battery.
The large specific capacity of silicon materials makes it a powerful candidate for the development of next generation high specific energy batteries. But the rapid charging capability of silicon materials at high currents has not reached the expectations of researchers and businesses, subject to their own electrical properties. Charge transfer is a major aspect that limits rapid charging of electrode materials. According to the energy band theory, electrons in the valence band pass through the forbidden band and enter the conduction band, so that the solid anode material is conductive. Therefore, in order to achieve rapid charging, a negative electrode material of high intrinsic electron conductivity is promising, such as carbon, metal or alloy with a small or zero band gap. However, silicon is a typical semiconductor material, which is much less conductive than commercial graphite materials. Even a single crystal silicon material having good conductivity is converted into amorphous silicon during lithium ion insertion/extraction, and its conductivity is deteriorated. In the conventional semiconductor process, the conductivity of the silicon material can be effectively improved by doping boron and phosphorus atoms. However, the original bonding state of the boron and phosphorus doped silicon material is broken in the lithium ion intercalation/deintercalation process, and the excellent electron conduction property of the boron and phosphorus doped silicon material is lost. Typical silicon-carbon negative electrode materials in the current commercial silicon-based negative electrode materials are prepared by coating carbon materials on the surfaces of nano silicon particles. The carbon material with better conductivity is coated on the surface of the silicon material, so that the charge transfer and transmission of the small-size nano silicon material can be improved. However, when the size of the silicon material increases, the poor conductivity of the bulk of the silicon material greatly limits the charge transfer in the silicon negative electrode material, so that the rapid charge and discharge energy of the silicon negative electrode material under a large current is very limited, and the rapid charge performance required by the power battery is difficult to realize. Therefore, overcoming a series of problems caused by volume expansion of a silicon material, particularly a large-size micro-nano silicon negative electrode material in the lithium ion insertion/extraction process, and improving the conductivity of a silicon material body is a key development of a silicon negative electrode lithium battery.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides the quick-charging silicon-based anode material for the lithium battery and the preparation method thereof, which effectively solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: the fast charging silicon-based negative electrode material for lithium battery consists of micro-nano silicon particles, buffering nanometer particle conducting channels embedded in the silicon particles and carbon shell conducting channels coated on the silicon particles.
Preferably, the dimensions of the silicon-based anode material comprise commercial silicon nano particles with the diameter of 20-30nm for lithium battery anode, micron particles with the diameter of 1 um-100 um, and micro-nano silicon particles with the diameter of 50 nm-100 um obtained by ball milling waste silicon materials in semiconductor process.
Preferably, the silicon-based anode material is a silicon-based material, comprising silicon monoxide, silicon dioxide and silicon oxide, and the size of the silicon-based anode material is silicon oxide nano particles with the commercial diameter of 20 nm-1000 nm for lithium battery anode, micron particles with the diameter of 1 um-100 um, and micro-nano silicon oxide particles with the diameter of 50 nm-100 um obtained by industrial ball milling of waste silicon waste materials in the semiconductor process.
Preferably, the nanoparticles include gold, silver, copper, iron, aluminum, nickel metal nanoparticles, alloy nanoparticles, and nonmetallic nanoscale particles, and the alloy nanoparticles include copper-silicon alloys, silver-silicon alloys, aluminum-silicon alloys, nickel-silicon alloys, iron-silicon alloys.
Preferably, the carbon shell layer comprises, but is not limited to, graphite, graphene, hard carbon, soft carbon, carbon black, acetylene black, ketjen black material,
The quick-charging silicon-based material is formed by compounding 5% -90% of silicon-based micro-nano particles, 5% -75% of metal-based nano particle conductive channels and 1% -20% of carbon shell conductive channels in percentage by mass;
the quick-charging silicon-based negative electrode is formed by compounding, by mass, 5% -85% of quick-charging silicon-based material, 3% -50% of conductive agent and 3% -15% of binder.
Preferably, the method comprises the steps of ball milling, preparing silicon monoxide by high-temperature pyrolysis, preparing silicon dioxide by magnesia reduction, and directly preparing the silicon-based material by hydrofluoric acid etching.
Preferably, the fast-charging silicon-based anode material also comprises other anode materials with high specific capacity, including one or more of alloy materials such as germanium, tin, phosphorus and the like and oxides thereof.
Preferably, the shell conductive channel further comprises a material of a type comprising one or more of a molybdenum sulfide two-dimensional material and a titanium dioxide intercalation material.
Preferably, the method is characterized in that: the preparation method of the quick-charging silicon-based anode material comprises the following steps:
Firstly, 50% -98% of the raw materials are mixed according to the mass ratio: 3% -20%: 5% -50% of mixed powder of micro-nano silicon particles, buffer nano particles and carbon is weighed, and is put into a ball mill to be uniformly mixed by 1600 rmin -1-1800 rmin-1 ball milling;
secondly, transferring the mixed materials into a sintering furnace, and annealing and sintering for 12 to 24 hours at 1200 to 1800 ℃;
Thirdly, coating a carbon shell layer material on the surface of the micro-nano silicon particles subjected to high-temperature sintering by adopting an industrial typical carbon coating method to obtain a silicon-based anode material, wherein the experimental parameters of carbon coating and the thickness of a coating layer can be referred to the parameters of coating carbon on the surface of the industrial silicon particles;
Weighing a certain mass of silicon-based anode material, and mixing the silicon-based anode material, an adhesive and a conductive agent according to a mass ratio of 7:1.5-2.0:1.5 to 1.0, fully mixing, putting into a ball mill, uniformly stirring, and then adding a solvent with certain mass, and uniformly stirring;
Fifthly, coating the mixed slurry on the copper foil by adopting a blade coating industry or an industrial coating process;
Sixthly, testing the assembled battery;
Or the following process preparation flow is adopted:
Firstly, 50% -98% of the raw materials are mixed according to the mass ratio: 3% -20%: 5% -50% of mixed powder of micro-nano silicon particles, buffer nano particles and carbon is weighed, and is put into a ball mill to be uniformly mixed by 1600 rmin -1-1800 rmin-1 ball milling;
transferring the mixed material into a sintering furnace, and sintering at 1200-1800 ℃ for 12-24 hours to obtain a silicon anode material;
thirdly, weighing a silicon-based anode material with a certain mass, and mixing the silicon-based anode material with an adhesive and a conductive agent according to a mass ratio of 7:1.5-2.0:1.5 to 1.0, fully mixing, putting into a ball mill, uniformly stirring, and then adding a solvent with certain mass, and uniformly stirring;
Fourthly, coating the mixed slurry on the copper foil by adopting a blade coating industry or an industrial coating process;
And fifthly, assembling a battery test.
Compared with the prior art, the invention has the beneficial effects that:
1) In the charge-discharge cycle process of the micro-nano silicon negative electrode material prepared by combining the process of embedding the buffer nano particle conductive channel and the process of coating the carbon shell conductive channel on the surface of the silicon particle, charges can be rapidly transferred and transmitted through the buffer nano particle conductive channel embedded in the silicon particle and the carbon shell coated on the surface of the silicon particle, so that the rapid charge-discharge capacity of the silicon negative electrode material under high current is improved.
2) The buffer nano particle conductive channel embedded in the silicon-based particles and the carbon shell conductive channel coated on the surfaces of the silicon-based particles can also play a role in relieving the volume change of the silicon-based particles, and are beneficial to improving the circulation stability of the silicon-based negative electrode;
3) The carbon shell on the surface not only can promote the charge transmission of the silicon-based particles, but also can stabilize the SEI film on the surface of the particles, thereby further improving the cycling stability of the silicon-based negative electrode.
4) The preparation process is compatible with the preparation process of the industrial lithium battery material.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic structural diagram of a fast-charging silicon anode material in an embodiment of the invention;
fig. 2 is a cycle-rate diagram of preparing a silicon anode material in an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses a quick-charging silicon-based anode material and a preparation method thereof, which are characterized in that: the quick-charging silicon-based negative electrode material consists of micro-nano scale silicon-based particles, buffer nano particle conductive channels embedded in the silicon-based particles and carbon shell conductive channels coated on the surfaces of the silicon-based particles, wherein the preparation process adopts a ball milling sintering process compatible with the industrial lithium battery preparation process.
Based on the ball milling sintering process compatible with the industrial lithium battery material preparation process, a buffer nanoparticle conductive channel is embedded in the micro-nano silicon-based particle bulk phase, and meanwhile, a carbon shell conductive layer is coated on the surface of the silicon-based particle to obtain the silicon-based negative electrode material capable of being charged and discharged rapidly. In the charge-discharge cycle process, charges can be rapidly transmitted through a buffer nanoparticle conductive channel embedded in the silicon-based particles and a carbon shell layer coated on the surfaces of the silicon particles, so that the rapid charge-discharge capacity of the silicon-based negative electrode under a large current is improved. Meanwhile, the buffer nanoparticle conductive channel embedded in the silicon-based particles and the carbon shell conductive channel coated on the surfaces of the silicon-based particles can also play a role in relieving the volume change of the silicon-based particles and stabilizing the SEI film on the surfaces of the particles, so that the cycling stability of the silicon-based negative electrode material is further improved.
The technical scheme of the invention is further defined as follows: the negative electrode material includes, but is not limited to, one or more of silicon (Si), germanium (Ge), phosphorus (P), tin (Sn), antimony (Sb), bismuth (Bi), aluminum (Al) and oxides thereof.
Further, the buffer nanoparticle conductive channel embedded in the silicon-based material body includes, but is not limited to, the buffer nanoparticle embedded in the silicon-based material body, and is characterized in that: the nanoparticles include, but are not limited to, gold (Au), silver (Ag), copper (Cu), iron (Fe), aluminum (Al), cobalt (Co), nickel (Ni), manganese (Mn), molybdenum (Mu), vanadium (V), and other metals and their oxide nanoparticles, at least one of gold-silicon (Au-Si), silver-silicon (Ag-Si), copper-silicon (Cu-Si), iron-silicon (Fe-Si), aluminum-silicon (Al-Si), nickel-silicon (Ni-Si), cobalt-silicon (Co-Si), nickel-silicon (Ni-Si), manganese-silicon (Mn-Si), molybdenum-silicon (Mu-Si), vanadium-silicon (V-Si), and other alloy nanoparticles, molybdenum (Mu), iron (Fe), tungsten (W), vanadium (V), and other disulfide nanoparticles of transition metals.
Further, the carbon shell conductive path includes, but is not limited to, the carbon shell conductive conduction, and is characterized in that: the shell conductive channel comprises at least one of carbon-based materials such as intercalated graphite, graphene, hard carbon, soft carbon, carbon black, acetylene black, ketjen black and the like, oxides such as layered titanium-based oxides, niobium-based oxides and the like, and sulfur-based compounds such as layered molybdenum-based sulfides and tungsten-based sulfides.
The rapid silicon charging negative electrode is formed by compounding 10% -90% of micro-nano silicon-based particle matrix, 3% -50% of nano particle conductive channels and 1% -50% of carbon shell conductive channels according to the structure shown in FIG. 1;
The invention also discloses a preparation method of the quick silicon-filled anode material, which is characterized in that: the preparation process of the quick-charging silicon-based anode material comprises at least one of ball milling sintering process, chemical vapor deposition method, high-temperature solid phase reaction method, mechanical alloying method, electrostatic spinning method and the like which are compatible with the preparation of the existing lithium battery anode material. The preparation flow of the typical process comprises the following steps:
Firstly, according to the mass ratio (50% -98%): (3% -20%): (5% -50%) weighing mixed powder of micro-nano silicon particles, buffer nano particles and carbon, and putting the mixed powder into a ball mill to be uniformly mixed by ball milling at 1600 rmin -1-1800 rmin-1%;
secondly, transferring the mixed materials into a sintering furnace, and annealing and sintering for 12 to 24 hours at 1200 to 1800 ℃;
And thirdly, coating a carbon shell material on the surface of the micro-nano silicon particles subjected to high-temperature sintering by adopting an industrially typical carbon coating method (such as a pyrolysis method, a ball milling method, a chemical vapor deposition method and the like) to obtain the silicon-based anode material. Wherein, the experimental parameters of carbon coating and the thickness of the coating can be referred to the parameters of coating carbon on the surface of industrial silicon particles.
Weighing a certain mass of silicon-based anode material, and mixing the silicon-based anode material, an adhesive and a conductive agent according to a mass ratio of 7: (1.5-2.0): (1.5 to 1.0) fully mixing, then placing the mixture into a ball mill, uniformly stirring, and then adding a solvent with certain mass and uniformly stirring;
And fourthly, coating the mixed slurry on the copper foil by adopting a blade coating industry or an industrial coating technology.
And fifthly, assembling a battery test.
Or the following process preparation flow is adopted:
Firstly, according to the mass ratio (50% -98%): (3% -20%): (5% -50%) weighing mixed powder of micro-nano silicon particles, buffer nano particles and carbon, and putting the mixed powder into a ball mill to be uniformly mixed by ball milling at 1600 rmin -1-1800 rmin-1%;
transferring the mixed material into a sintering furnace, and sintering at 1200-1800 ℃ for 12-24 hours to obtain a silicon anode material;
Thirdly, weighing a silicon-based anode material with a certain mass, and mixing the silicon-based anode material with an adhesive and a conductive agent according to a mass ratio of 7: (1.5-2.0): (1.5 to 1.0) fully mixing, then placing the mixture into a ball mill, uniformly stirring, and then adding a solvent with certain mass and uniformly stirring;
And fourthly, coating the mixed slurry on the copper foil by adopting a blade coating industry or an industrial coating technology.
And fifthly, assembling a battery test.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A quick-charging silicon-based negative electrode material for a lithium battery is characterized in that: the silicon-based anode material consists of micro-nano silicon-based particles, buffer nano particle conductive channels embedded in the silicon-based particles and carbon shell conductive channels coated on the surfaces of the silicon-based particles;
the silicon-based anode material comprises commercial silicon nano particles with the diameter of 20-30nm for lithium battery anode, silicon micro particles with the diameter of 1-100 mu m and micro nano silicon particles with the diameter of 50-100 mu m obtained by ball milling of waste silicon waste materials of semiconductor process, or comprises silicon oxide nano particles with the diameter of 20-1000 nm for lithium battery anode, silicon oxide micro particles with the diameter of 1-100 mu m and micro nano silicon oxide particles with the diameter of 50-100 mu m obtained by ball milling of waste silicon waste materials of semiconductor process;
the buffer nanoparticle comprises at least one of a metal nanoparticle and an alloy nanoparticle, the metal nanoparticle comprises at least one of gold, silver, copper, iron, aluminum and nickel, and the alloy nanoparticle comprises at least one of copper-silicon alloy, silver-silicon alloy, aluminum-silicon alloy, nickel-silicon alloy and iron-silicon alloy;
The preparation method of the quick-charging silicon-based anode material comprises the following steps:
Firstly, 50% -98% of the raw materials are mixed according to the mass ratio: 3% -20%: 5% -50% of mixed powder of micro-nano silicon-based particles, buffer nano particles and carbon is weighed, and is put into a ball mill to be ball-milled and mixed uniformly at a speed of 1600rmin -1 -1800 rmin -1;
and secondly, transferring the mixed materials into a sintering furnace, and annealing and sintering for 12 to 24 hours at the temperature of 1200 to 1800 ℃.
2. The rapid charging silicon-based anode material for lithium batteries according to claim 1, wherein: the carbon shell layer comprises at least one of graphite, graphene, hard carbon, soft carbon, acetylene black and ketjen black.
3. The rapid charging silicon-based anode material for lithium batteries according to claim 1, wherein: the rapid charging silicon-based anode material also comprises one or more than two of germanium, tin, phosphorus and oxides thereof.
4. The rapid charging silicon-based anode material for lithium batteries according to claim 1, wherein: the carbon shell conductive channel also comprises one or two of molybdenum sulfide two-dimensional material and titanium dioxide intercalation material.
5. The method for preparing the quick-charging silicon-based anode material for the lithium battery, which is characterized in that:
the method comprises the following steps:
Firstly, 50% -98% of the raw materials are mixed according to the mass ratio: 3% -20%: 5% -50% of mixed powder of micro-nano silicon-based particles, buffer nano particles and carbon is weighed, and is put into a ball mill to be ball-milled and mixed uniformly at a speed of 1600rmin -1 -1800 rmin -1;
Secondly, transferring the mixed materials into a sintering furnace, and annealing and sintering for 12 to 24 hours at the temperature of 1200 to 1800 ℃;
thirdly, coating a carbon shell layer material on the surface of the micro-nano silicon-based particles subjected to high-temperature sintering by adopting a carbon coating method of a pyrolysis method, a ball milling method or a chemical vapor deposition method to obtain a quick-charging silicon-based anode material;
Weighing the quick-charging silicon-based anode material, and mixing the quick-charging silicon-based anode material, an adhesive and a conductive agent according to the mass ratio of 7:1.5-2.0:1.5 to 1.0, fully mixing, putting into a ball mill, uniformly stirring, and then adding a solvent and uniformly stirring;
Fifthly, coating the mixed slurry on the copper foil by adopting a coating process;
and sixthly, assembling a battery test.
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