CN109713286A - A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery - Google Patents

A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery Download PDF

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CN109713286A
CN109713286A CN201811652600.0A CN201811652600A CN109713286A CN 109713286 A CN109713286 A CN 109713286A CN 201811652600 A CN201811652600 A CN 201811652600A CN 109713286 A CN109713286 A CN 109713286A
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silica
particle
base material
silicon
lithium
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CN109713286B (en
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罗姝
汪芳
查道松
李喆
王岑
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Boselis Hefei Co ltd
Bosellis Nanjing Co ltd
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Ann Price (nanjing) Co Ltd
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Abstract

The silicon based composite material and preparation method thereof that the present invention relates to a kind of for lithium ion secondary battery includes the silica-base material particle with lithium ion, and silica-base material particle has core-shell structure, and particle is coated with composite film；Composite film is divided into two layers: internal layer is the carbon film/conductive additive composite film for being completely covered or partially covering the carbon film layer or carbon film layer and conductive additive formation of silica-base material particle surface；Outer layer is partially crystallizable or the metallic compound clad being fully crystallized, which is completely covered or part covers the surface of foregoing silicon substrate material granule or the surface of aforementioned internal layer；The formation of the core-shell structure of the silica-base material particle is to spread because of are as follows: aforementioned metal compound clad toward silica-base material particle surface layer, with particle surface layer ining conjunction with, fine and close shell of the formation containing metal silicate compound.Silicon based composite material of the invention is used for lithium ion secondary battery, have the characteristics that capacity is high, coulombic efficiency height, have extended cycle life, water resistance it is strong.

Description

A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery
Technical field
The present invention relates to field of lithium ion secondary, and in particular to a kind of silicon based composite material and preparation method thereof.
Background technique
In recent years, it with the continuous development of various portable electronic devices and electric car, for energy density height, follows The demand of the lithium ion battery of ring service life length is increasingly urgent to.The negative electrode material of current commercialized lithium ion battery is mainly stone Ink, but since theoretical capacity is low (372mAh/g), limit further increasing for lithium ion battery energy density.And elemental silicon is negative Pole material then has very high capacity advantage, and (embedding lithium state is Li at room temperature15Si4, theoretical lithium storage content about 3600mAh/g), it is mesh 10 times or so of preceding commercial graphite negative electrode material theoretical capacity, the high capacity advantage that there are other negative electrode materials can not be equal to, because This becomes the research and development focus of academia and industrial circle for many years, and gradually from laboratory, business application is moved towards in research and development.Needle at present To there are mainly three types of the exploitations of silicium cathode material, first is that elemental silicon (including nano-silicon, porous silicon, amorphous silicon etc.) and its same carbon materials The composite material of material；Second is that silicon and other metals (such as iron, manganese, nickel, chromium, cadmium, tin, copper), nonmetallic (carbon, nitrogen, phosphorus, boron etc.) The alloy material that ingredient is composed；Third is that silicon oxide compound and its composite material with carbon material.It is single in three of the above structure The theoretical capacity highest of matter silicon materials, therefore theoretical energy density also highest.However, elemental silicon negative electrode material is in embedding de- lithium process In there are serious bulk effect, volume change is about 300%, will cause electrode material dusting and electrode material and afflux Body separation.In addition, due to constantly dilation and the lasting rupture in battery charge and discharge process of silicium cathode material, generation it is new Fresh interface, which is exposed to, will form new SEI film in electrolyte, to persistently consume electrolyte, reduce the cyclicity of electrode material Energy.Drawbacks described above seriously limits the commercial applications of simple substance silicium cathode.Silicon oxide compound is due to wherein with more non-live Property substance, cause its capacity lower than elemental silicon negative electrode material；However simultaneously as the presence of these inactive ingredients (usually Silica or silicate patterns), expansion of the silicon in cyclic process is effectively inhibited by nonactive phase, therefore its cyclical stability has It has a clear superiority.For elemental silicon, silicon oxide compound is easier to realize industrial applications.However, silicon oxide compound there is also Its specific problem.In embedding lithium for the first time, particle surface often generates the material since more side reaction occurs with electrolyte Thicker SEI film；Meanwhile particle inside can generate lithium metasilicate and lithia etc. can not reversible de- lithium (positive lithium metasilicate Li4SiO4 is removed Substance outside) causes the irreversible loss of lithium ion in battery.Above-mentioned two classes irreversible reaction leads to cathode containing silicon oxide compound Lithium ion battery coulombic efficiency is lower (theoretical efficiency is about 70%) for the first time, to limit mentioning for full battery energy density It rises.Meanwhile although expansion of silicon oxide compound during removal lithium embedded has been significantly lower than simple substance silicium cathode, silicon oxide compound Rupture and its caused electrolyte consumption of the grain during long circulating can still occur, which also limits it and recycle conservation rate Promotion.In addition, coulombic efficiency is more low during silicon oxide compound there is also ions and electronic conductivity lower, circulating battery Problem.Based on the above issues, scientific research personnel has carried out the improvement of following aspect.
Specifically, in order to improve the electric conductivity of silicon oxide compound, it, can to obtain high capacity and preferably circulation conservation rate The conductive materials such as cladding carbon film on silicon oxide compound surface layer.And in order to improve the particle inner conductive of silicon oxide compound, it can be right Its progress is metal-doped.In order to improve first charge-discharge efficiency, pre-doping lithium can be carried out to silicon oxide compound, including silicon is aoxidized It closes object and lithium metal carries out high-temperature mixing (such as patent document CN103840136A and CN104471757A), or use electrochemistry side Method aoxidizes silicon and closes cathode progress preliminary filling lithium (such as patent document CN104979524A), or makes silicon oxygen using high energy mechanical mixing Compound with as lithiumation agent lithium metal or organo-lithium compound mix while react in situ (such as patent document CN101047234B), also or make lithium-containing compound (lithium hydride, lithium hydroxide, lithium carbonate, lithia, organo-lithium compound Deng) with react under silicon oxide compound high temperature, realize to the preliminary filling lithium of silicon oxide compound.Due to the presence of lithium-containing compound, Stronger alkalinity is often presented in such material, causes the water resistance of material lower.Therefore, in the water system homogenate of actual battery production In the process, if using the negative electrode material for containing such siliceous oxygen lithium compound, slurry is easy to happen since material alkalinity is higher Denaturation；Simultaneously as the water resistance of siliceous oxygen lithium compound is poor, it is easy to react with water, matter when slurry being caused to be coated with It is lower to measure poor and yield rate.
Application publication number is that the Chinese patent of CN107710466A has disclosed a kind of siliceous oxygen lithium compound negative electrode material And its manufacturing method.There are one layer of carbon coating and one layer of amorphous metal oxide and metallic hydrogen in the siliceous oxygen lithium compound surface The composite layer that oxide is constituted, the composite layer which is constituted is to pass through gold Belong to alkoxide hydrolysis and dehydrating condensation and formed.The stability that the negative electrode material is homogenized water system as a result, is improved. In the material structure, although amorphous metal oxide and metal hydroxides composite layer can improve the resistance to of material to a certain degree It is aqueous, but structure is more loose after all for noncrystalline composite layer, it is not fine and close enough, therefore, amorphous metal oxide and metallic hydrogen Oxide cladding layers have the following problems: 1) short texture, and the permeability of electrolyte is high, can not inhibit silicon oxide compound particle table The side reaction in face and electrolyte；2) water absorption rate that short texture also results in clad improves, easy absorbing and storing water in clad Point, cause silicon oxygen lithium compound unstable in daily storage instead, leads to the denaturation and chemical property decline of material；3) Amorphous clad is difficult to effectively obstruct contact of the moisture with silicon base compound, in water system homogenization process, the oxidation of silicon containing lithium Object is closed due to poor water resistance, easily reacts with moisture, leads to the loss of active material, also leads to denaturation and the coating pole of slurry The deterioration of tablet quality.In addition, that is announced in the patent prepares amorphous metal oxide and metal hydroxides composite layer Method has used the metal alkoxide of cost costly, is being contained by the hydrolysis and dehydrating condensation that control metal alkoxide Silicon oxygen lithiumation object surface in situ coated metal oxide and metal hydroxides composite layer, the process control difficulties are higher, required Time cost is larger, is unfavorable for scale application at low cost.
Summary of the invention
The capacity that in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of for lithium ion secondary battery is high, Coulombic efficiency is high, have extended cycle life, water resistance is strong, can be used water system homogenate system silicon based composite material and its can scale system Standby method.
To achieve the above object, present invention provide the technical scheme that
A kind of silicon based composite material, includes the silica-base material particle with lithium ion, and the silica-base material particle has Core-shell structure, silica-base material particle are coated with composite film；The composite film is divided into two layers: internal layer is to be completely covered or portion Divide the carbon film layer of covering silica-base material particle surface or carbon film/conductive additive composite membrane of carbon film layer and conductive additive formation Layer；Outer layer is partially crystallizable or the metallic compound clad being fully crystallized, which is completely covered or partially covers aforementioned The surface of silica-base material particle or the surface of aforementioned internal layer；The formation of the core-shell structure of the silica-base material particle be because are as follows: it is preceding It states metallic compound clad to spread toward silica-base material particle surface layer, in conjunction with particle surface layer, formation contains metal metasilicate The fine and close shell of salt compound.
The metallic compound clad is by one in metal oxide or basic metal oxide or metal hydroxides Kind or different materials composition, include one of titanium, magnesium, zirconium, zinc, copper, aluminium, nickel, iron, manganese, cobalt, chromium, calcium, barium, tin or a variety of Element.The metallic compound clad is partially crystallizable or is fully crystallized that the clad structure is finer and close as a result,.Meanwhile It is preferred that the clad with a thickness of 1-20nm.In this thickness range, which can effectively obstruct silica-base material particle It is contacted with moisture or the direct of electrolyte, improves the water-resistant stability and coulombic efficiency, while its electricity for the first time of silicon based composite material Resistance can be controlled in lesser range, will not electro-chemical activity to material and cyclical stability adversely affect.
The silica-base material particle has core-shell structure, contains other metals member in addition to lithium in the shell of core-shell structure Element, the metallic element is identical as the metallic element in above-mentioned metallic compound clad, and the formation of the core-shell structure is Cause are as follows: above-mentioned metallic compound clad is spread toward silica-base material particle surface layer, in conjunction with the original structure in particle surface layer, is formed Fine and close " shell " containing metal silicate compound.This fine and close " shell " structure further can be obstructed effectively in particle The contact in portion and outside moisture or electrolyte avoids material and water in water system homogenization process and reacts and causes active constituent Loss inhibits the release (reducing pH value) of the alkalinity of silica-base material containing lithium, while its surface can form more stable SEI film, pole The big coulombic efficiency and capacity stability for improving material in battery charging and discharging cyclic process.
For the median particle diameter of the silica-base material particle between 0.2-20 μm, the silica-base material particle also includes uniform The simple substance nano silicon particles of dispersion are scattered in the median particle diameter of the simple substance nano silicon particles in silica-base material particle in 0.1-35nm Between.For above-mentioned particle when undergoing the circulation of lithium ion insertion abjection, the expansion that particle occurs is smaller and is not easily broken as a result,. Carbon film layer or carbon film/conductive additive composite film thickness outside the silica-base material particle is between 0.001-5 μm；It is described Silica-base material particle in, silicon content 49.89-79.89wt%, oxygen element content 20-50wt%, elemental lithium content For 0.1-20wt%,；In the carbon film layer, the ratio between carbon film and silica-base material particle weight are 0.01: 100-20: 100；It is described Carbon film/conductive additive composite film in, the ratio between carbon film and silica-base material particle weight are 0.01: 100-20: 100, conductive The ratio between additive and silica-base material particle weight are 0: 100-10: 100.
Above-mentioned carbon film layer or the presence of carbon film/conductive additive composite film can effectively improve the conductivity of particle, drop In low cathode pole piece between particle, the contact resistance of cathode pole piece and collector reduces to improve the removal lithium embedded efficiency of material The polarization of lithium ion battery simultaneously promotes its cyclical stability.Further, since insertion is a large amount of in advance inside the silica-base material particle Lithium ion, therefore compared with traditional silicon oxide compound negative electrode material, the coulombic efficiency for the first time and circulation of the silica-base material containing lithium are protected Holdup is significantly improved.
In addition, in the silica-base material particle can also contain a small amount of doped chemical, the doped chemical be P, F, N, S, the combination of one or more of B, Mg, Al, Ca, Cu, B, Fe, Mn, Zn, Zr, Ti, Sn, doped chemical content are 0.01- 10wt%.
In addition, in the forming step of aforementioned metal compound clad, preferably are as follows: reactant is the water-soluble of aforementioned metal Property or alcohol-soluble compound, such as nitrate, nitrite, sulfate, sulphite, disulfate, hydrophosphate, di(2-ethylhexyl)phosphate The inorganic metal salts and acetate, oxalates, citrate etc. such as hydrogen salt, haloid (chloride, bromide, iodide etc.) Organic metal salt.Silica-base material particle is dispersed in the aqueous solution or alcoholic solution or water alcohol mixed liquor of above-mentioned metal salt, wherein The dispersion concentration range of silica-base material particle in the solution is 5wt%-70wt%；The concentration range of metal ion in the solution is 0.001mol/L-2mol/L.Precipitation reaction or hydrolysis by soluble metal ion in solution, are realized in silicon Sill particle surface in extremely rapid succession coated metal oxide or basic metal oxide or metal hydroxides clad.Together When, in order to regulate and control the Precipitation reaction or hydrolysis speed of metal ion, to regulate and control the uniformity and shape of clad Sustained release agent, such as surfactant, sodium citrate, oxalic acid, hydrochloric acid, acetic acid can be added in looks during the reaction.In order to further The crystallinity of metallic compound clad is improved, while clad being promoted to spread toward silica-base material particle surface layer, it need to be by above-mentioned step Suddenly the material obtained is heat-treated in vacuum or nonoxidizing atmosphere, and heat treatment temperature is 150-700 DEG C, and soaking time is 0.1-12 hours, heating rate was greater than 1 DEG C per minute, per minute less than 100 DEG C.By the step particles cladded by metallic compound film layer After subsequent heat treatment technique, the weight of silica-base material particle be will increase, and weight gain ranges preferably from 0.1-10wt%.Above-mentioned technique Process is simple controllable, at low cost, reproducible, and required equipment is simple, is suitble to large-scale industrial production.It is above-mentioned heat treated Cheng Zhong, the metallic compound clad of particle surface in addition to obviously being optimized in crystallinity, ingredient it can also happen that variation, Metal hydroxides may be dehydrated to form basic metal oxide or metal oxide, and basic metal oxide may also be into one Step dehydration forms metal oxide；Meanwhile above-mentioned metallic compound clad is spread toward silica-base material particle endosexine, with particle The original structure in surface layer combines, and forms the metal silicate compound of compact structure.
The present invention also protects the lithium ion battery negative material prepared using above-mentioned silicon based composite material, with above-mentioned lithium Ion battery cathode material prepares negative electrode of lithium ion battery, and the lithium-ion electric prepared with above-mentioned negative electrode of lithium ion battery Pond.
Compared with the prior art, the invention has the following advantages:
1. the silicon based composite material in the invention has three-layer protection layer, one layer contains gold for silica-base material particle outer layer The compact outer shell layer of category silicate, one layer of carbon film layer or carbon film/conductive additive composite layer for silica-base material particle outer cladding, One layer is outermost partially crystallizable or the finer and close metallic compound clad of the structure that is fully crystallized.This three-layer protection layer can Effectively to obstruct the contact inside particle with moisture, stability of the material in daily storage, especially raising material are improved Water resistance in water system homogenization process avoids silicon nanoparticle and water generation air-generating reaction inside particle from causing active material Loss；Meanwhile three layers of fine and close protective layer inhibit the release of the alkalinity of silica-base material containing lithium, reduce the pH value of material, it will not The rheological equationm of state and stability of slurry are influenced, therefore is effectively prevented in coating process because producing gas, slurry rheological property and stability The pole pieces quality problems such as uneven, the bonding difference of pole piece pin hole, pit caused by deterioration, surface density.
2. above-mentioned three layers of fine and close protective layer can also completely cut off internal nano silicon particles and extraneous electrolyte, itself and electricity are reduced The side reaction that liquid occurs is solved, while more stable SEI film can be formed, material is greatly improved in battery charging and discharging cyclic process Coulombic efficiency and capacity stability.
3. the characteristic of compound, such as high coulombic efficiency, high reversible capacity, good circulation conservation rate, circulation expansion are small Electrochemical properties are also perfectly retained in material structure of the invention.And use lithium ion two prepared by the material Primary cell also has the advantages that energy density height, good cycling stability, expansion are low.
To sum up, there is capacity height, coulombic efficiency when silicon based composite material of the invention is used as negative electrode of lithium ion battery High, good cycle electrochemical properties.The lithium ion battery of the silicon based composite material preparation has energy density height, circulation The characteristic that stability is good, expansion is low.The preparation method of the silicon based composite material is simple, at low cost, reproducible, required equipment Simply, can large-scale industrial production, and the materials water-resistant is good, can directly apply to the water system cathode that industry generallys use It is homogenized process system, can really realize the scale application containing silicium cathode in field of lithium ion battery.
Detailed description of the invention
Fig. 1 is 50000 times of stereoscan photographs of silicon based composite material prepared by embodiment 1.
Fig. 2 is the cycle performance figure of the full battery containing silicium cathode prepared by embodiment 1.
Specific embodiment
Hereinafter, illustrating embodiment for the present invention, but the present invention is not limited to this embodiments.
Silicon based composite material provided in the present invention includes the silica-base material particle with lithium ion.The silicon substrate Silicon and oxygen element stoichiometric ratio in material granule are 1: 0.5-1: 1.5.The silica-base material particle surface is coated with carbon film Carbon film/conductive additive composite film that layer or carbon film layer and conductive additive are formed.The silica-base material particle surface cladding Carbon film layer or carbon film/conductive additive composite film structure can be accomplished in the following manner:
The carbon film layer can be directly obtained by way of chemical vapor deposition, or by first carrying out carbon reaction cladding again The mode that heat treatment carbonization is carried out in nonoxidizing atmosphere obtains.The carbon film/conductive additive composite film passes through following Mode obtains: the silicon oxide compound particle for having been subjected to chemical vapor deposition progress carbon film coated reacts mixed with conductive additive and carbon After conjunction, then heat treatment carbonization is carried out in nonoxidizing atmosphere；Or silicon oxide compound particle is reacted with conductive additive and carbon After mixing, then heat treatment carbonization is carried out in nonoxidizing atmosphere and is obtained.The packet of the carbon reaction or carbon reaction and conductive additive Coating method uses any one in mechanical fusion machine, VC mixing machine, cladding kettle, spray drying, sand mill or high speed disperser, The solvent selected when cladding be water, methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, ether, acetone, N-Methyl pyrrolidone, Espeleton, tetrahydrofuran, benzene,toluene,xylene, n,N-Dimethylformamide, n,N-dimethylacetamide, in chloroform One or more combinations.The carbon reaction is selected from coal tar pitch and petroleum asphalt, polyvinyl alcohol, epoxy resin, polyacrylonitrile, gathers One of methyl methacrylate, glucose, sucrose, polyacrylic acid, polyvinylpyrrolidone or a variety of combinations.It is described to lead Electric additive is Super P, Ketjen black, gas-phase growth of carbon fibre, acetylene black, electrically conductive graphite, carbon nanotube, one in graphene Kind or a variety of combinations.The heat treatment carbonization device therefor is rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tubular type Any one in furnace.The temperature of the heat treatment carbonization is 500-1200 DEG C, and soaking time is 0.5-24 hours.It is described non-oxygen Change atmosphere to be provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.
In addition, the heretofore described silica-base material particle with lithium ion, is mixed by carrying out lithium to silicon oxide compound Miscellaneous modified acquisition, specific lithium doping method of modifying include electrochemical method, liquid phase doping methods, hot doping method, high-temperature mixing Method, high energy mechanical method etc..Wherein, preferably electrochemical method, liquid phase doping methods and hot doping method.
When modified using electrochemical method progress lithium doping, it is desirable to provide an electrochemical cell, wherein including bath, anode Four electrode, cathode electrode and power supply components, and anode electrode and cathode electrode are separately connected the both ends of power supply.Meanwhile anode Electrode connects lithium source, and cathode electrode connection includes the container of silicon oxide compound particle.Full organic solvent is filled in bath, Make lithium source (anode electrode) and includes that the container (cathode electrode) of silicon oxide compound particle is immersed in organic solvent.Connect electricity Behind source, due to the generation of electrochemical reaction, lithium ion is embedded in silicon oxide compound structure, obtains the modified silica-base material of lithium doping Particle.Ethylene carbonate, propene carbonate, butylene, fluorinated ethylene carbonate, carbonic acid two can be used in above-mentioned organic solvent Methyl esters, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, propyl acetate, ethyl propionate, propyl propionate, dimethyl sulfoxide etc. are molten Agent.In addition, also containing electrolyte lithium salt in the organic solvent, lithium hexafluoro phosphate (LiPF can be used6), LiBF4 (LiBF4), lithium perchlorate (LiClO4) etc..Lithium foil or lithium compound can be used in above-mentioned lithium source (anode electrode), such as lithium carbonate, oxygen Change lithium, lithium hydroxide, cobalt acid lithium, LiFePO4, LiMn2O4, phosphoric acid vanadium lithium, lithium nickelate etc..
It is modified in addition, liquid phase doping methods also can be used and carry out lithium doping to silicon oxide compound.When it is implemented, by metal Lithium, Electron-Transfer Catalyst, silicon oxide compound particle are added in ether-based solvent, persistently stir in nonoxidizing atmosphere and heat guarantor Isothermal reaction is held, until the lithium metal in solution completely disappears.Under the action of Electron-Transfer Catalyst, lithium metal can dissolve In ether-based solvent, and the complex of lithium ion is formed, there is lower reduction potential, therefore can send out with silicon oxide compound Raw reaction, lithium ion enter in silicon oxide compound structure.The Electron-Transfer Catalyst includes biphenyl, naphthalene etc..The ether is molten Agent includes methyl butyl ether, butyl glycol ether, tetrahydrofuran, glycol dimethyl ether etc..The isothermal reaction temperature is 25-120 ℃.The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.
It is modified in addition, hot doping method also can be used and carry out lithium doping to silicon oxide compound.It is closed when it is implemented, silicon is aoxidized Composition granule is uniformly mixed with lithium-containing compound, is then heat-treated in nonoxidizing atmosphere.The lithium-containing compound includes hydrogen Lithia, lithium carbonate, lithia, lithium peroxide, lithium hydride, lithium nitrate, lithium acetate, lithium oxalate etc..The mixed method uses High speed disperser, high-speed stirred mill, ball mill, cone-type mixer, mixing screw, in stirring-type mixing machine or VC mixing machine Any one.The heat treatment device therefor is any in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace It is a kind of.The temperature of the heat treatment is 400-1000 DEG C, and soaking time is 0.1-12 hours, and heating rate is greater than 1 DEG C per minute, Per minute less than 100 DEG C.The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.
In addition, heretofore described silica-base material particle, can be P containing a small amount of doped chemical, the doped chemical, F, the combination of one or more of N, S, B, Mg, Al, Ca, Cu, B, Fe, Mn, Zn, Zr, Ti, Sn.Specific doping way packet It includes: 1) when coating carbon film layer or cladding carbon film/conductive additive composite film, while element being carried out to silicon oxide compound particle Doping；2) before carrying out lithium doping, preferentially silicon oxide compound particle uniformly mixed with dopant and in non-oxide gas After carrying out heat treatment doping in atmosphere, then lithium doping is carried out, wherein the dopant is simple substance or chemical combination containing doped chemical Object powder；3) lithium doping and other elements doping vario-property are carried out simultaneously to the silicon oxide compound.The mixed method is using high Fast dispersion machine, high-speed stirred mill, ball mill, cone-type mixer, mixing screw, appointing in stirring-type mixing machine or VC mixing machine It anticipates one kind.The heat treatment device therefor is any one in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace Kind.The temperature of the heat treatment is 400-1000 DEG C, and soaking time is 0.1-12 hours, and heating rate is greater than 1 DEG C per minute, small Per minute in 100 DEG C.The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.
In addition, there are also one layer of partially crystallizable or the metal compounds being fully crystallized for heretofore described silica-base material particle surface Object clad, the clad are that metal oxide or one or more of basic metal oxide or metal hydroxides are tied Structure is constituted, and includes one of titanium, magnesium, zirconium, zinc, copper, aluminium, nickel, iron, manganese, cobalt, chromium, calcium, barium, tin or multiple element.
In the forming step of above-mentioned clad, reactant is the water solubility or alcohol-soluble chemical combination of above-mentioned metallic element Object, such as sulfate, sulphite, disulfate, hydrophosphate, dihydric phosphate, nitrate, nitrite, haloid (chlorination Object, bromide, iodide etc.) etc. organic gold such as inorganic metal salts and acetate, oxalates, butyl, citrate Belong to salt.Specifically, silica-base material particle to be dispersed in the aqueous solution or alcoholic solution or water alcohol mixed liquor of above-mentioned metal salt first In.Wherein the dispersion concentration range of silicon oxygen lithium compound in the solution is 5wt%-70wt%；Metal ion in the solution dense Degree range is 0.001mol/L~2mol/L.Precipitation reaction or hydrolysis by soluble metal ion in solution, It realizes in silica-base material particle surface in extremely rapid succession coated metal oxide or basic metal oxide or metal hydroxides Clad.Meanwhile in order to regulate and control the reaction of the Precipitation of metal ion or hydrolysis speed, to regulate and control the uniform of clad Property and pattern, can be added sustained release agent, such as surfactant (lauryl sodium sulfate, detergent alkylate sulphur during the reaction Sour sodium), sodium citrate, oxalic acid, hydrochloric acid, acetic acid etc..In order to further increase the crystallinity of metallic compound clad, promote simultaneously It spreads clad toward silica-base material particle surface layer, the material that above-mentioned steps obtain need to be carried out in vacuum or nonoxidizing atmosphere Heat treatment, heat treatment temperature are 150-700 DEG C, and soaking time is 0.1-12 hours, and heating rate is greater than 1 DEG C per minute, are less than 100 DEG C per minute.Above-mentioned heat treatment device therefor is appointing in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace It anticipates one kind.The non-oxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.Above-mentioned heat treatment In the process, the metallic compound clad of particle surface in crystallinity in addition to obviously being optimized, and ingredient is it can also happen that become Change, metal hydroxides may be dehydrated to form basic metal oxide or metal oxide, and basic metal oxide may also Further dehydration forms metal oxide；Meanwhile above-mentioned metallic compound clad is spread toward silica-base material particle endosexine, with The original structure in particle surface layer combines, and forms the metal silicate compound of compact structure.This layer of fine and close metal silicate Compound is for example same hard " shell ", the silicon nanoparticle that can be effectively isolated inside silica-base material particle and foreign objects The reaction of matter greatly improves the stability of material.
Embodiment 1
The silicon oxide compound particle (silicone atom ratio is 1: 1) and 70g low temperature coal tar pitch for being 6 μm by 1000g median particle diameter Powder cladding kettle in dry mixed it is uniform after, while stirring be added 2000g dimethylformamide, by mixed-powder in dimethyl It is uniformly dispersed in formamide.Then heating cladding kettle to 140 DEG C and keeps constant temperature to stir 3 hours, is finally again heated to 160 DEG C simultaneously Constant temperature obtains the silicon oxide compound material of coal tar pitch cladding up to dimethylformamide to be evaporated.By above-mentioned material in nitrogen atmosphere It is heated to 900 DEG C under enclosing and keeps making coal tar pitch be carbonized in 4 hours, while disproportionated reaction occurs for silicon oxide compound.It will be obtained after cooling To material cross 500 mesh screens, obtain the silicon oxide compound powder of carbon film coated.
In drying room of the relative humidity lower than 30%, powder that 500 grams of above-mentioned steps are obtained, 50 grams of metal lithium bands, 10 grams of biphenyl are added in a salable glass container, and 1000 grams of methyl butyl ethers are then added and a large size stirs magneton. At this point, being sealed after argon gas being filled in container, and container is placed on magnetic stirring apparatus and is stirred, revolving speed is set as 200r/min.After reaction 5 hours, after the methyl butyl ether in container is evaporated or filters removal, lithium doping is can be obtained in drying Silicon oxygen lithium compound powder.
The material obtained after 500 grams of above-mentioned steps is taken, being added into 1 liter of volumetric concentration is 0.02mol/L (writing a Chinese character in simplified form 0.02M) Zirconium oxychloride aqueous solution in, persistently stir 2 as a child after, powder is separated with solution in the way of suction filtration, after drying must Amorphous state zirconium hydroxide/zirconium oxide film layer silicon oxygen lithium particle is coated with to surface.The product is further put into vacuum drying oven Middle heat treatment, in the state of persistently vacuumizing, 150 DEG C of heat preservations are heat-treated 4 hours, and taking out after cooling down can be obtained final production Object.It is analyzed, is found after the step coating modification by weighing, material has increased weight 0.5wt%.Fig. 1 show embodiment 1 The electron scanning micrograph of final products, 50000 times of amplification factor, it can clearly be seen that silicon oxygen lithium particle surface is coated with One layer of fine and close complete zirconium oxygen compound clad.It is characterized by further transmission electron microscope, the zirconium of particle surface The thickness of oxygen compound clad is about 3nm, and clad is partially crystallizable.
The method cut using focused ion beam, has obtained the section sample of above-mentioned silicon substrate composite particles.In Scanning Electron Under microscope, it can be clearly seen that silicon oxygen lithium particle surface has coated the carbon film layer that a layer thickness is about 60m.Outermost gold Belong to compound clad since thickness is too thin, under the sample preparation of section sample and characterization method, is not easy to differentiate instead.It is dissipated using back Penetrate analysis and X-ray energy spectrum analysis, it can be seen that in the inside of carbon film layer, the i.e. outer layer of silicon lithia particle, there is very thin one " shell " layer of layer containing zr element, illustrates that zirconium oxygen compound clad part has been diffused into the surface layer of silica-base material particle.
Above-mentioned silicon based composite material is mixed with deionized water, uses the Accurate pH of Ohaus Instrument (Shanghai) Co., Ltd. Tester, the pH value that can measure the dispersion liquid is 10.9.
Take 10 parts of above-mentioned silicon based composite material, 85 parts of artificial graphite, 2.5 parts of conductive additive, 2.5 parts of binder, in water Property system under be homogenized, take partial stream homogenate slurry to do water resistance and stability test, then other slurries are dried for being coated with It does, roll, obtain siliceous cathode pole piece.
Aqueous slurry stability assessment containing above-mentioned silicon based composite material: the above-mentioned water system homogenate slurry of 30g is taken to be stored in 65 DEG C, and confirm when above-mentioned slurry starts to produce gas with this condition.Under this harsh conditions, above-mentioned slurry can adhere to 72 hours Do not produce gas.In conventional water system homogenization process, slurry temperature is typically maintained in 30-40 DEG C.Therefore, slurry used by this patent The evaluating method of stability, harsh degree have far surmounted the condition of practical water system homogenate coating production process.In this evaluating method Under, if slurry can adhere to not producing gas in 24 hours, it is believed that the silicon based composite material water resistance in the slurry is strong, stability is good, It can be used for large-scale water system homogenate.
Half-cell assessment: above-mentioned siliceous cathode pole piece and diaphragm, lithium piece, stainless steel gasket are successively stacked and 200 μ are added dropwise 2016 formula lithium ion half-cells are made in sealing after L electrolyte.With small (micro-) electric current of Lan electricity electronics limited liability company, Wuhan City Range equipment test capacity and discharging efficiency.The de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 446mAh/ G, first charge-discharge efficiency (de- lithium stopping potential 0.8V) is 90.2%.
Full battery assessment: above-mentioned siliceous cathode pole piece passes through cutting, vacuum bakeout, together with the positive plate of pairing and diaphragm After being wound and putting into plastic-aluminum shell of corresponding size, a certain amount of electrolyte and deairing and sealing are injected, one is obtained after chemical conversion The siliceous negative electrode lithium ion full battery of a about 3.2Ah.It should with the cell tester test of new Weir Electronics Co., Ltd., Shenzhen Capacity, average voltage of the full battery at 0.2C, and capacity retention ratio number is obtained charge and discharge cycles 500 times under 0.7C multiplying power According to.Thus the volume energy density for obtaining full battery is 762Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 83%. Fig. 2 is the cycle performance figure of the full battery containing silicium cathode prepared by embodiment 1.
Embodiment 2
Compared to embodiment 1,2 silicon oxide compound particles coat carbon technology of embodiment uses chemical vapour deposition technique, with Acetylene is that carbon reaction carries out completing for 3 hours at 900 DEG C；Meanwhile the technique of subsequent particles cladded by metallic compound film layer is also Change, wherein the input amount of silicon oxygen lithium particle is still 500 grams, and reaction solution is changed are as follows: volumetric concentration is four fourth of 0.1M metatitanic acid The water of ester adds alcohol mixed solution, wherein water: ethyl alcohol 1: 50 (mass ratio), and the input amount of reaction solution is 2.5L, subsequent thermal Treatment process is same as Example 1.Other materials preparation process and evaluation method are same as Example 1.Gained silicon substrate is compound Material is after coating titanium oxygen compound film layer, and mass weight gain is about 2wt%, the titanium oxygen compound film layer of particle outermost layer cladding Thickness is about 14nm, and has one layer very thin " shell " layer containing titanium elements inside particle.Gained silicon based composite material PH value be 10.7, evenly dispersed silicon nanocrystal particle size is about 4.5nm inside particle.Water containing the silicon substrate composite particles System's homogenate slurry can adhere to not producing gas in 72 hours under 65 DEG C of Acceleration studies.Finally measure the half-cell containing silicium cathode for the first time Reversible de- lithium specific capacity is 439mAh/g, first charge-discharge efficiency 90.4%.The volume energy density for measuring full battery reaches 758Wh/L, the capacity retention ratio after 500 charge and discharge cycles are 83.1%.
Embodiment 3
Compared to embodiment 1, embodiment 3 carries out asphalt to silicon oxide compound powder using the VC mixing machine of hot type Cladding, and pitch input amount is changed to 50g, and the heat treatment condition after pitch-coating silicon oxide compound particle is changed to 3 at 900 DEG C Hour.Then, silicon oxide compound particle above-mentioned steps obtained is added in electrochemical reaction cell, using electrochemical method to silicon Oxygen compound realizes lithium doping, after lithium doping amount reaches 10wt%, stops reaction, obtains silicon oxygen lithium compound.Then, to upper When stating silica-base material particles coat metallic compound film layer, technique has carried out following change compared to embodiment 1: reaction solution changes Add alcohol mixed solution for the water that volumetric concentration is 0.05M magnesium nitrate, wherein water: ethyl alcohol 1: 1 (mass ratio), reaction solution Input amount is 2L, and subsequent heat treatment technique is same as Example 1.Other materials preparation process and evaluation method with embodiment 1 It is identical.For gained silicon based composite material after coating magnesia compound film layer, mass weight gain is about 1wt%, particle outermost layer cladding The thickness of magnesia compound film layer be about 7nm, and there is one layer very thin " shell " layer containing magnesium elements inside particle. The pH value of gained silicon based composite material is 10.9, and evenly dispersed silicon nanocrystal particle size is about 3.8nm inside particle.Contain this The water system homogenate slurry of silicon substrate composite particles can adhere to not producing gas in 72 hours under 65 DEG C of Acceleration studies.It finally measures siliceous negative The de- lithium specific capacity reversible for the first time of the half-cell of pole is 443mAh/g, first charge-discharge efficiency 90.5%.Measure the body of full battery Product energy density reaches 761Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 85%.
Embodiment 4
10 will be added simultaneously when embodiment 4 carries out asphalt cladding to silicon oxide compound powder compared to embodiment 3 Gram multi-walled carbon nanotube, obtained silicon oxide compound particle surface are uniformly distributed carbon nanotube and pitch-coating object.By 900 DEG C After 3 hours carbonization treatments, the uniform enveloped carbon nanometer tube/carbon film layer of silicon oxide compound particle surface.Above-mentioned carbon nanotube/carbon film The silicon oxide compound particle of layer cladding to mix lithium technique same as Example 3.Then, to above-mentioned silica-base material particles coat metal When compound film layer, technique has carried out following change compared to embodiment 3: it is 0.1M aluminum nitrate that reaction solution, which is changed to volumetric concentration, Ethanol solution, the input amount of reaction solution is 2L, and subsequent heat treatment technique is same as Example 3.Other materials preparation process It is same as Example 3 with evaluation method.After coating aluminum oxide film layer, mass weight gain is about gained silicon based composite material The thickness of 1.5wt%, the aluminum oxide film layer of particle outermost layer cladding are about 11nm, and are had inside particle one layer very thin " shell " layer containing aluminium element.The pH value of gained silicon based composite material is 10.8, evenly dispersed silicon nanometer inside particle Crystallite dimension is about 3.8nm.Water system homogenate slurry containing the silicon substrate composite particles can adhere to that 72 is small under 65 DEG C of Acceleration studies When do not produce gas.The de- lithium specific capacity reversible for the first time for finally measuring the half-cell containing silicium cathode is 441mAh/g, first charge-discharge effect Rate 90.4%.The volume energy density for measuring full battery reaches 759Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 85.2%.
Embodiment 5
Compared to embodiment 4, embodiment 5 does not add multi-walled carbon nanotube, but is added and leads while coating pitch Electric carbon black.Meanwhile the lithium doping method of silicon oxide compound particle is changed to hot doping method, specifically: taking 500 grams of above-mentioned claddings Conductive black/carbon film layer silicon oxide compound particle mixes 57 grams of lithium hydrides, mixed-powder is placed in tube furnace, in argon Atmosphere is heat-treated under enclosing, and is kept for 180 minutes after being warming up to 800 DEG C with the heating rate of 10 DEG C/min, will after natural cooling Material takes out from tube furnace and crosses 500 mesh screens, obtains silicon oxygen lithium compound.Then, to above-mentioned silica-base material particles coat When metallic compound film layer, technique has carried out following change compared to embodiment 4: it is 0.15M that reaction solution, which is changed to volumetric concentration, The water of copper acetate adds alcohol mixed solution, wherein water: ethyl alcohol 1: 1 (mass ratio), and the input amount of reaction solution is 1L, subsequent thermal Processing still uses vacuum drying oven, and heat treatment process is changed to lower 150 DEG C of vacuum condition and is heat-treated 8 hours.Other materials preparation process It is same as Example 4 with evaluation method.After coated copper oxygen compound film layer, mass weight gain is about gained silicon based composite material The thickness of 2wt%, the copper oxygen compound film layer of particle outermost layer cladding are about 13nm, and are had inside particle one layer very thin " shell " layer containing copper.The pH value of gained silicon based composite material is 10.4, evenly dispersed silicon nanocrystal inside particle Particle size is about 6.5nm.Water system homogenate slurry containing the silicon substrate composite particles can adhere to 72 hours under 65 DEG C of Acceleration studies Do not produce gas.The de- lithium specific capacity reversible for the first time for finally measuring the half-cell containing silicium cathode is 446mAh/g, first charge-discharge efficiency 91.2%.The volume energy density for measuring full battery reaches 770Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 84.5%.
Embodiment 6
Compared to embodiment 5, embodiment 6 uses sucrose instead as carbon film layer coating reaction, and Super P is as conductive addition Agent, ferro element is as doped chemical.Specific preparation method be by 1000g silicon oxide compound particle, 10gSuper P powder, Slurry is carried out spray drying treatment after the dispersion of 5000g deionized water high speed by 289.6g Fe(NO3)39H2O and 50g sucrose, Then under nitrogen atmosphere by obtained powder, 900 DEG C heating 3 hours after be crushed and cross 500 mesh screens.It is obtained above The Fe2O3 doping silicon oxide compound particle of Super P/ carbon film layer cladding to mix lithium technique same as Example 5.Then, to above-mentioned silicon When sill particles coat metallic compound film layer, technique has carried out following change compared to embodiment 5: reaction solution is changed to body Product concentration is that the water of 0.01M zirconium oxychloride adds alcohol mixed solution, wherein water: ethyl alcohol 1: 1 (mass ratio), the throwing of reaction solution Entering amount is 500mL, and subsequent heat treatment still uses vacuum drying oven, and it is small that heat treatment process is changed to the lower 200 DEG C of heat treatment 4 of vacuum condition When.Other materials preparation process and evaluation method are same as Example 5.Gained silicon based composite material is in cladding zirconium oxygen compound After film layer, mass weight gain is about 0.1wt%, and the thickness of the zirconium oxygen compound film layer of particle outermost layer cladding is about 1nm, and particle Inside has one layer very thin " shell " layer containing zr element.The pH value of gained silicon based composite material is 11, inside particle Evenly dispersed silicon nanocrystal particle size is about 6nm.Water system homogenate slurry containing the silicon substrate composite particles is real in 65 DEG C of acceleration It tests down, can adhere to not producing gas in 24 hours.The de- lithium specific capacity reversible for the first time for finally measuring the half-cell containing silicium cathode is 436mAh/ G, first charge-discharge efficiency 91.6%.The volume energy density for measuring full battery reaches 766Wh/L, after 500 charge and discharge cycles Capacity retention ratio be 84.3%.
Embodiment 7
Compared to embodiment 6, embodiment 7 has changed doped chemical into copper, obtains using with the similar technique of embodiment 6 The Copper-cladding Aluminum Bar silicon oxide compound particle of Super P/ carbon film layer cladding, subsequent to mix lithium technique also same as Example 6.Then, right When above-mentioned silica-base material particles coat metallic compound film layer, technique has carried out following change: reaction solution compared to embodiment 6 Be changed to the water that volumetric concentration is 0.03M zirconium oxychloride and add alcohol mixed solution, wherein water: ethyl alcohol 1: 1 (mass ratio) reacts molten The input amount of liquid is 500mL, and subsequent heat treatment technique is same as Example 6.Other materials preparation process and evaluation method with Embodiment 6 is identical.Gained silicon based composite material is after coating zirconium oxygen compound film layer, and mass weight gain is about 0.3wt%, and particle is most The thickness of the zirconium oxygen compound film layer of external sheath is about 2nm, and is had inside particle one layer very thin containing zr element " shell " layer.The pH value of gained silicon based composite material is 10.9, and evenly dispersed silicon nanocrystal particle size is about inside particle 8nm.Water system homogenate slurry containing the silicon substrate composite particles can adhere to not producing gas in 48 hours under 65 DEG C of Acceleration studies.Finally The de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 429mAh/g, first charge-discharge efficiency 91.6%.It measures The volume energy density of full battery reaches 760Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 84.8%.
Embodiment 8
Compared to embodiment 5, when embodiment 8 carries out asphalt cladding to silicon oxide compound powder, pitch additional amount increases 70g is added to, and that any conductive additive is not added；Meanwhile using hot doping method to the silicon oxide compound for being coated with carbon film layer When carrying out lithium doping, take 51g lithium hydride blending 17g lithium borohydride as lithium source, simple lithium hydride in alternate embodiment 5, together Lithium doping and boron doping of the Shi Shixian to silicon oxide compound.Then, it metallizes to above-mentioned boron doped silica-base material particles coat When compound film layer, technique has carried out following change compared to embodiment 5: it is 0.05M oxychlorination that reaction solution, which is changed to volumetric concentration, The water of zirconium adds alcohol mixed solution, wherein water: ethyl alcohol 1: 1 (mass ratio), and the input amount of reaction solution is 1L；Subsequent heat treatment Using tube furnace, one end closure of tube furnace, another termination vacuum pump, in the state of persistently vacuumizing, tube furnace with 20 DEG C/ The speed of min is warming up to 250 DEG C, keeps the temperature 8 hours, takes out material after then cooling to room temperature with the furnace, obtain final products.Other Material preparation process and evaluation method are same as Example 5.Gained silicon based composite material after coating zirconium oxygen compound film layer, Mass weight gain is about 1wt%, and the thickness of the zirconium oxygen compound film layer of particle outermost layer cladding is about 5nm, and is had inside particle One layer very thin " shell " layer containing zr element.The pH value of gained silicon based composite material is 10.3, is uniformly divided inside particle Scattered silicon nanocrystal particle size is about 5.1nm.Water system containing the silicon substrate composite particles is homogenized slurry under 65 DEG C of Acceleration studies, Can adhere to not producing for one week gas (can actually adhere to not producing the gas time may be longer, and the longest testing time of the test is set as one week, It removes after a week).The de- lithium specific capacity reversible for the first time for finally measuring the half-cell containing silicium cathode is 452mAh/g, first charge-discharge Efficiency 92%.The volume energy density for measuring full battery reaches 781Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 86%.
Embodiment 9
Compared to embodiment 8, embodiment 9 is changed to 1000 DEG C to the carbonization heat treatment process after pitch-coating silicon oxide compound Lower 2 hours；Meanwhile when carrying out lithium doping and other elements doping to silicon oxide compound using hot doping method, 57g lithium hydride is taken to mix Mixed 5g calcium hydride realizes lithium doping and calcium analysis to silicon oxide compound as lithium source and calcium source.Then, to above-mentioned calcium analysis When silica-base material particles coat metallic compound film layer, technique has carried out following change compared to embodiment 8: reaction solution is changed to Volumetric concentration is that the water of 0.08M zirconium oxychloride adds alcohol mixed solution, wherein water: ethyl alcohol 1: 1 (mass ratio), reaction solution Input amount is 1.5L；Subsequent heat treatment still uses tube furnace, is continually fed into the state of argon gas, and tube furnace is with the speed of 10 DEG C/min Degree is warming up to 500 DEG C, keeps the temperature 2 hours, takes out material after then cooling to room temperature with the furnace, obtain final products.Other materials system Standby technique and evaluation method are same as Example 8.After coating zirconium oxygen compound film layer, quality increases gained silicon based composite material Weigh about as 3wt%, the thickness of the zirconium oxygen compound film layer of particle outermost layer cladding is about 8nm, and have inside particle one layer compared with Thin while thickness is greater than " shell " layer containing zr element of embodiment 8.The pH value of gained silicon based composite material is 9.4, The evenly dispersed silicon nanocrystal particle size in intragranular portion is about 5.2nm.Water system homogenate slurry containing the silicon substrate composite particles is 65 Under DEG C Acceleration study, it can adhere to not producing for one week gas (can actually adhere to do not produce the gas time may be longer).Finally measure containing silicium cathode Half-cell de- lithium specific capacity reversible for the first time be 442mAh/g, first charge-discharge efficiency 92.1%.Measure the volume of full battery Energy density reaches 774Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 84.8%.
Embodiment 10
Compared to embodiment 5, when embodiment 10 carries out asphalt cladding to silicon oxide compound powder, pitch additional amount increases 70g is added to, and that any conductive additive is not added；Meanwhile when carrying out lithium doping to silicon oxide compound using hot doping method, hydrogen The incorporation for changing lithium is improved to 85 grams, and will be mixed lithium heat treatment temperature and be changed to 750 DEG C, and holding time was to 5 hours.Then, When to above-mentioned silica-base material particles coat metallic compound film layer, technique has carried out following change compared to embodiment 5: reaction is molten Liquid is changed to the water that volumetric concentration is 0.2M zirconium oxychloride and adds alcohol mixed solution, wherein water: ethyl alcohol 1: 1 (mass ratio), reaction The input amount of solution is 1L；Subsequent heat treatment uses tube furnace, is continually fed into the state of argon gas, tube furnace is with 10 DEG C/min's Speed is warming up to 700 DEG C, keeps the temperature 2 hours, takes out material after then cooling to room temperature with the furnace, obtain final products.Other materials Preparation process and evaluation method are same as Example 5.Gained silicon based composite material is after coating zirconium oxygen compound film layer, quality Weight gain is about 5wt%, and the thickness of the zirconium oxygen compound film layer of particle outermost layer cladding is about 6nm, and has one layer inside particle Relatively thin while thickness is greater than " shell " layer containing zr element of embodiment 8 and embodiment 9.Gained silicon based composite material PH value is 9.2, and evenly dispersed silicon nanocrystal particle size is about 4.4nm inside particle.Water system containing the silicon substrate composite particles Slurry is homogenized under 65 DEG C of Acceleration studies, can adhere to not producing for one week gas (can actually adhere to do not produce gas time possibility longer).Finally The de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 437mAh/g, first charge-discharge efficiency 92.3%.It measures The volume energy density of full battery reaches 771Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 85.6%.
Embodiment 11
Compared to embodiment 10, the lithium hydride incorporation of embodiment 11 is down to 40 grams, and will mix the raising of lithium heat treatment temperature It is 850 DEG C, soaking time was reduced to 1 hour.When then, to above-mentioned silica-base material particles coat metallic compound film layer, work Skill has carried out following change compared to embodiment 10: reaction solution is changed to the water that volumetric concentration is 0.1M magnesium nitrate and adds ethyl alcohol mixing molten Liquid, wherein water: ethyl alcohol 1: 1 (mass ratio), the input amount of reaction solution are 1L；Subsequent heat treatment uses tube furnace, tube furnace One end closure, another termination vacuum pump, in the state of persistently vacuumizing, tube furnace is warming up to 350 with the speed of 20 DEG C/min DEG C, 2 hours are kept the temperature, material is taken out after then cooling to room temperature with the furnace, obtains final products.Other materials preparation process and evaluation Method is same as in Example 10.After coating magnesia compound film layer, mass weight gain is about gained silicon based composite material The thickness of 1wt%, the magnesia compound film layer of particle outermost layer cladding are about 4nm, and are had inside particle one layer very thin " shell " layer containing magnesium elements.The pH value of gained silicon based composite material is 9.8, evenly dispersed silicon nanocrystal inside particle Size is about 8.2nm.Water system homogenate slurry containing the silicon substrate composite particles can adhere to not producing for one week under 65 DEG C of Acceleration studies Gas (can actually adhere to do not produce gas time may longer).Finally measure the de- lithium specific capacity reversible for the first time of the half-cell containing silicium cathode For 443mAh/g, first charge-discharge efficiency 91.8%.The volume energy density for measuring full battery reaches 771Wh/L, 500 charge and discharges Capacity retention ratio after electricity circulation is 83.4%.
Embodiment 12
Compared to embodiment 11, the lithium hydride incorporation of embodiment 12 is improved to 57 grams, and will be mixed lithium heat treatment temperature and be changed It is 2 hours at 850 DEG C.When then, to above-mentioned silica-base material particles coat metallic compound film layer, technique compares embodiment 11 Carried out following change: reaction solution is changed to the water that volumetric concentration is 0.05M magnesium chloride and adds alcohol mixed solution, wherein water: second Alcohol is 1: 1 (mass ratio), and the input amount of reaction solution is 1L；Subsequent heat treatment uses tube furnace, is continually fed into the state of argon gas Under, tube furnace is warming up to 500 DEG C with the speed of 10 DEG C/min, and 2 hours are kept the temperature, takes out material after then cooling to room temperature with the furnace, Obtain final products.Other materials preparation process and evaluation method are identical as embodiment 11.Gained silicon based composite material is wrapping After covering magnesia compound film layer, mass weight gain is about 0.5wt%, and the thickness of the magnesia compound film layer of particle outermost layer cladding is about For 1nm, and there is one layer very thin " shell " layer containing magnesium elements inside particle.The pH value of gained silicon based composite material is 10.1, the evenly dispersed silicon nanocrystal particle size in particle inside is about 12.4nm.Water system homogenate containing the silicon substrate composite particles Slurry can adhere to not producing for one week gas (can actually adhere to do not produce the gas time may be longer) under 65 DEG C of Acceleration studies.Finally measure The de- lithium specific capacity reversible for the first time of half-cell containing silicium cathode is 448mAh/g, first charge-discharge efficiency 92.4%.Measure full electricity The volume energy density in pond reaches 781Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 83%.
Embodiment 13
Compared to embodiment 11, the lithium hydride incorporation of embodiment 13 is improved to 85 grams, and will be mixed lithium heat treatment temperature and be changed It is 3 hours at 850 DEG C.When then, to above-mentioned silica-base material particles coat metallic compound film layer, technique compares embodiment 11 Carried out following change: reaction solution is changed to the water that volumetric concentration is 0.1M magnesium sulfate and adds alcohol mixed solution, wherein water: ethyl alcohol For 1: 1 (mass ratio), the input amount of reaction solution is 1L；Subsequent heat treatment uses tube furnace, is continually fed into the state of argon gas, Tube furnace is warming up to 700 DEG C with the speed of 10 DEG C/min, keeps the temperature 2 hours, takes out material after then cooling to room temperature with the furnace, obtain Final products.Other materials preparation process and evaluation method are identical as embodiment 11.Gained silicon based composite material is in cladding magnesium After oxygen compound film layer, mass weight gain is about 1wt%, and the thickness of the magnesia compound film layer of particle outermost layer cladding is about 1nm, And " shell " layer containing magnesium elements that inside particle there is one layer very thin while thickness to be thicker than embodiment 11.Gained silicon The pH value of based composites is 10.1, and evenly dispersed silicon nanocrystal particle size is about 16.8nm inside particle.Contain the silicon substrate The water system homogenate slurry of composite particles can adhere to that not producing within one week gas (can actually adhere to not producing the gas time under 65 DEG C of Acceleration studies It may be longer).The de- lithium specific capacity reversible for the first time for finally measuring the half-cell containing silicium cathode is 451mAh/g, first charge-discharge effect Rate 92.9%.The volume energy density for measuring full battery reaches 788Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 82.1%.
Comparative example 1
Technical process similar embodiment 1, difference is not carry out lithium doping, also without subsequent cladding metal compound The process of object film layer, therefore product is the silicon oxygen with carbon film layer cladding that film layer is coated without containing elemental lithium and metallic compound Compound particle.The pH value of gained silicon based composite material is 7.8, and evenly dispersed silicon nanocrystal particle size is about inside particle 3.2nm.Water system homogenate slurry containing the silicon substrate composite particles can adhere to not producing a gas under 65 DEG C of Acceleration studies.Finally The de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 466mAh/g, first charge-discharge efficiency 84.5%.It measures The volume energy density of full battery reaches 715Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 84.2%.Due to right In the material of ratio 1 do not contain elemental lithium, the negative electrode material charge for the first time in lithium ion battery embedding lithium when will form silicic acid Lithium based compound or lithia cause higher lithium ion irreversible loss, to cause first charge-discharge efficiency low, in turn Cause the energy density of full battery lower.
Comparative example 2
Technical process similar embodiment 1, difference are the process of no subsequent particles cladded by metallic compound film layer, therefore Product is the silica-base material particle with carbon film layer cladding of not metal-containing compound coating film layer.Gained silicon based composite material PH value is 12.2, and evenly dispersed silicon nanocrystal particle size is about 4.5nm inside particle.Water system containing the silicon substrate composite particles Slurry is homogenized under 65 DEG C of Acceleration studies, can only adhere to not producing within 2 hours gas, subsequent slurry generates a large amount of bubbles, and pulp flow Property be deteriorated, be easy agglomeration, cause application difficulties.Finally measuring the de- lithium specific capacity reversible for the first time of the half-cell containing silicium cathode is 448mAh/g, first charge-discharge efficiency 89.7%.The volume energy density for measuring full battery reaches 756Wh/L, 500 charge and discharge Capacity retention ratio after circulation is 81%.Since the material of comparative example 2 does not have particles cladded by metallic compound film layer, while its internal silicon Sill particle lacks the compact outer shell layer containing metal silicate, therefore the alkalinity release of material is unable to get inhibition, pH value It is very high, it easily causes slurry denaturation and mobility is deteriorated.In addition, the material surface lacks the protective layer that can effectively obstruct moisture, Air-generating reaction occurs for the moisture and particle interior contact being homogenized in slurry, causes application difficulties, and active material quality is significantly damaged It loses.
Comparative example 3
Technical process similar embodiment 5, difference are the process of no subsequent particles cladded by metallic compound film layer, therefore Product is the silica-base material particle of not metal-containing compound coating film layer coated with conductive black/carbon film layer.Gained silicon substrate The pH value of composite material is 11.3, and evenly dispersed silicon nanocrystal particle size is about 6.5nm inside particle.It is compound containing the silicon substrate The water system of particle is homogenized slurry under 65 DEG C of Acceleration studies, can only adhere to not producing within 2 hours gas, and subsequent slurry generates a large amount of bubbles, And slurry fluidity is deteriorated, and is easy agglomeration, causes application difficulties.Finally measure the de- lithium reversible for the first time of the half-cell containing silicium cathode Specific capacity is 455mAh/g, first charge-discharge efficiency 90.6%.The volume energy density for measuring full battery reaches 769Wh/L, and 500 Capacity retention ratio after secondary charge and discharge cycles is 83.3%.
Comparative example 4
Technical process similar embodiment 13, difference are that silica-base material particle surface does not coat carbon film layer, also do not have The process of subsequent particles cladded by metallic compound film layer, therefore product is the silicon substrate that film layer is coated without carbon film layer and metallic compound Material granule.The pH value of gained silicon based composite material is 11.9, and evenly dispersed silicon nanocrystal particle size is about inside particle 16.8nm.Water system containing the silicon substrate composite particles is homogenized slurry under 65 DEG C of Acceleration studies, can only adhere to not producing gas in 2 hours, Subsequent slurry generates a large amount of bubbles, and slurry fluidity is deteriorated, and is easy agglomeration, causes application difficulties.Finally measure containing silicium cathode Half-cell de- lithium specific capacity reversible for the first time be 445mAh/g, first charge-discharge efficiency 89.2%.Measure the volume of full battery Energy density reaches 742Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 74.8%.Material in comparative example 4 does not have Carbon film layer or carbon film/conductive agent composite film cladding, cause its electric conductivity poor, while particle surface is also not easy to be formed surely Fixed SEI, therefore it is poor to recycle conservation rate.
Comparative example 5
Technical process similar embodiment 10, unique difference are that the metallic compound film layer of particle surface cladding is not undergone Subsequent 700 DEG C of heat treatment processes.The quality accounting of the zirconium oxygen compound clad on gained silicon substrate composite particles surface layer is about 5wt%, thickness are about 50nm.Through X-ray diffraction analysis and tem study it is found that the zirconium of particle extexine cladding Oxygen compound is non crystalline structure.Through further cross-section analysis it is found that under the process conditions of the comparative example, particle extexine The zirconium oxygen compound of cladding toward silica-base material particle endosexine without spreading, therefore silica-base material particle lacks containing metal metasilicate Densification " shell " layer of salt.The pH value of gained silicon substrate composite particles is 10.2, evenly dispersed silicon nanocrystal ruler inside particle Very little about 4.4nm.Water system homogenate slurry containing the silicon substrate composite particles can adhere to not producing for 12 hours under 65 DEG C of Acceleration studies Gas, subsequent slurry start to generate bubble.The de- lithium specific capacity reversible for the first time for finally measuring the half-cell containing silicium cathode is 436mAh/ G, first charge-discharge efficiency 89%.The volume energy density for measuring full battery reaches 733Wh/L, after 500 charge and discharge cycles Capacity retention ratio is 78.8%.Material in comparative example 5 is not due to having experience follow-up heat treatment process, surface coated zirconium oxygen Compound film layer is non crystalline structure, more loose, and zirconium oxygen compound clad is not spread to silica-base material particle endosexine, because This cladding thicknesses of layers is up to 50nm.It, can not fully effective isolation moisture and inside since the cladding film layer structure is not fine and close enough The contact of silicon nanoparticle, therefore the water resistance of material is general, the stability that water system is homogenized slurry is also general.In addition, due to The zirconium oxygen compound thicknesses of layers of material surface is thicker, causes its electric conductivity poor, the battery polarization in charge and discharge process also can Cause the problems such as efficiency for charge-discharge is low, capacity is low low with circulation conservation rate.
Comparative example 6
Technical process similar embodiment 12, unique difference are that the metallic compound film layer of particle surface cladding is not undergone Subsequent 500 DEG C of heat treatment processes.The quality accounting of the magnesia compound clad on gained silicon substrate composite particles surface layer is about 0.5wt%, thickness are about 6nm, while its internal silica-base material particle lacks densification " shell " layer containing metal silicate.Institute The pH value for obtaining silicon substrate composite particles is 10.9, and evenly dispersed silicon nanocrystal particle size is about 12.4nm inside particle.Contain this The water system homogenate slurry of silicon substrate composite particles can only adhere to not producing within 4 hours gas, subsequent slurry generates big under 65 DEG C of Acceleration studies Bubble is measured, and slurry fluidity is deteriorated, is easy agglomeration, causes application difficulties.Finally measure the half-cell containing silicium cathode for the first time Reversible de- lithium specific capacity is 448mAh/g, first charge-discharge efficiency 92%.The volume energy density for measuring full battery reaches 764Wh/L, the capacity retention ratio after 500 charge and discharge cycles are 82.1%.
Comparative example 7
Technical process similar embodiment 4, difference are the metallic compound film layer of silica-base material particle surface cladding (150 DEG C of heat treatment process of subsequent vacuum remain unchanged) is significantly increased in quality accounting and thickness.Gained silicon based composite material exists After coating aluminum oxide film layer, mass weight gain is about 7wt%, and the thickness of the aluminum oxide film layer of particle outermost layer cladding is about For 45nm, and there is one layer very thin " shell " layer containing aluminium element inside particle.The pH value of resulting materials is 9.6, The evenly dispersed silicon nanocrystal particle size in intragranular portion is about 3.8nm.Water system homogenate slurry containing the silicon substrate composite particles is 65 Under DEG C Acceleration study, it can adhere to not producing for one week gas (can actually adhere to do not produce the gas time may be longer).Finally measure containing silicium cathode Half-cell de- lithium specific capacity reversible for the first time be 416mAh/g, first charge-discharge efficiency 89%.Measure the volume energy of full battery Metric density reaches 718Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 78.1%.Material surface in comparative example 7 Cladding film layer is thicker, and electric conductivity is poor, causes it to recycle conservation rate lower.
Comparative example 8
Technical process similar embodiment 10, it is subsequent after difference is silica-base material particles coat metallic compound film layer Heat treatment process change, heat treatment temperature is improved to keeping the temperature 2 hours at 900 DEG C.Gained silicon based composite material is coating After zirconium oxygen compound film layer and experience subsequent heat treatment, mass weight gain is about 5wt%, characterizes and finds through scanning electron microscope, outside particle Layer is hardly visible metallic compound cladding film layer, it was demonstrated that the zirconium oxygen compound of particle surface cladding has almost diffused to completely Intragranular portion.At such a temperature, the zirconium oxygen compound of silicon oxygen lithium particle surface cladding is toward when spreading inside particle, not only diffusing to Intragranular surface layer forms the compact outer shell layer for being rich in zr element, can also spread toward particle inner core, the aggregation segregation rich in zr element Obstruction of meeting and reduction lithium ion cause its cycle performance poor in intragranular diffusion.It is obtained by X-ray diffraction analysis The distribution of silicon nanocrystal particle size concentrates on 19nm and 40nm inside particle.Finally measure the reversible for the first time of the half-cell containing silicium cathode De- lithium specific capacity is 420mAh/g, first charge-discharge efficiency 92%.Measure full battery volume energy density be 740Wh/L, 500 Capacity retention ratio after secondary charge and discharge cycles is 72.8%.In addition, the pH value of resulting materials is 9.1 in comparative example 8, contain the silicon The water system homogenate slurry of base composite particles can adhere to not producing a gas under 65 DEG C of Acceleration studies.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention It is interior.

Claims (8)

1. a kind of silicon based composite material for lithium ion secondary battery, it is characterised in that: include the silicon substrate with lithium ion Material granule, the silica-base material particle have core-shell structure, and silica-base material particle is coated with composite film；The composite membrane Layer is divided into two layers: internal layer is that the carbon film layer for being completely covered or partially covering silica-base material particle surface or carbon film layer are added with conductive Dosage form at carbon film/conductive additive composite film；Outer layer is partially crystallizable or the metallic compound clad being fully crystallized, and is somebody's turn to do Clad is completely covered or part covers the surface of foregoing silicon substrate material granule or the surface of aforementioned internal layer；The silica-base material The formation of the core-shell structure of grain is to spread because of are as follows: aforementioned metal compound clad toward silica-base material particle surface layer, with Grain surface layer combines, and forms the fine and close shell containing metal silicate compound.
2. the silicon based composite material according to claim 1 for lithium ion secondary battery, it is characterised in that: the metal Compound clad is formed by metal oxide or one or more of basic metal oxide or metal hydroxides material, Include one of titanium, magnesium, zirconium, zinc, copper, aluminium, nickel, iron, manganese, cobalt, chromium, calcium, barium, tin or multiple element；The metal compound Object clad with a thickness of 1-20nm.
3. the silicon based composite material according to claim 1 for lithium ion secondary battery, it is characterised in that: the silicon substrate For the median particle diameter of material granule between 0.2-20 μm, the silica-base material particle also includes evenly dispersed elemental silicon nanometer Particle is scattered in the median particle diameter of the simple substance nano silicon particles in silica-base material particle between 0.1-35nm；The silicon substrate Carbon film layer or carbon film/conductive additive composite film thickness outside material granule is between 0.001-5 μm；The silica-base material In particle, silicon content 49.89-79.89wt%, oxygen element content 20-50wt%, elemental lithium content are 0.1- 20wt%；The ratio between carbon film and silica-base material particle weight are 0.01: 100-20: 100；The ratio between carbon film and silica-base material particle weight It is 0.01: 100-20: 100；The ratio between conductive additive and silica-base material particle weight are 0: 100-10: 100.
4. the silicon based composite material according to claim 1 for lithium ion secondary battery, it is characterised in that: the silicon substrate In material granule also contain a small amount of doped chemical, the doped chemical be P, F, N, S, B, Mg, Al, Ca, Cu, B, Fe, Mn, The combination of one or more of Zn, Zr, Ti, Sn, doped chemical content are 0.01-10%.
5. the preparation method described in claim any one of 1-4 for the silicon based composite material of lithium ion secondary battery, feature It is, comprising the following steps:
1) preparation surface is coated with carbon film layer or carbon film/conductive additive composite film silicon oxide compound or contains doped chemical Silicon oxide compound particle；
2) it is modified that the silicon oxide compound particle obtained to step 1) carries out lithium doping, or carries out lithium doping simultaneously and other elements are mixed Miscellaneous modification；
3) metallic compound clad is formed in the silica-base material particle surface that step 2) obtains, and after formation clad, it is described Metallic compound clad can be spread toward silica-base material particle surface layer, in conjunction with particle surface layer.
6. the preparation method for the silicon based composite material of lithium ion secondary battery as claimed in claim 5, which is characterized in that In step 3):
Reactant is water-soluble or alcohol-soluble inorganic metal salt or organic metal salt；
The silica-base material particle is dispersed in the aqueous solution or alcoholic solution or water alcohol mixed liquor of above-mentioned metal salt, wherein silicon substrate The dispersion concentration range of material granule in the solution is 5wt%-70wt%；The concentration range of metal ion in the solution is 0.001mol/L~2mol/L；Sustained release agent can be added in reaction solution；
Precipitation reaction or hydrolysis by soluble metal ion in solution, are realized in silica-base material particle surface In extremely rapid succession coated metal oxide or basic metal oxide or metal hydroxides clad；After being covered to complete, need by Material is further heat-treated under vacuum atmosphere or non-oxidizing atmosphere；
The heat treatment temperature is 150-700 DEG C, and soaking time is 0.1-12 hours, and heating rate is greater than 1 DEG C per minute, is less than 100 DEG C per minute；
The nonoxidizing atmosphere is provided by following at least one gases: nitrogen, argon gas, hydrogen or helium.
7. a kind of negative electrode of lithium ion battery, it is characterised in that: include the described in any item silicon based composite materials of claim 1-4.
8. a kind of lithium ion battery, it is characterised in that: prepared using negative electrode of lithium ion battery as claimed in claim 7.
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