CN108461723A - A kind of silicon based composite material and preparation method thereof for lithium ion battery - Google Patents

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

Info

Publication number
CN108461723A
CN108461723A CN201810140725.9A CN201810140725A CN108461723A CN 108461723 A CN108461723 A CN 108461723A CN 201810140725 A CN201810140725 A CN 201810140725A CN 108461723 A CN108461723 A CN 108461723A
Authority
CN
China
Prior art keywords
lithium
silicon
silica
compound particle
carbon film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810140725.9A
Other languages
Chinese (zh)
Other versions
CN108461723B (en
Inventor
李喆
汪芳
王岑
赵志伟
叶兰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boselis Hefei Co ltd
Bosellis Nanjing Co ltd
Original Assignee
Ann Price (nanjing) Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ann Price (nanjing) Co Ltd filed Critical Ann Price (nanjing) Co Ltd
Priority to CN201810140725.9A priority Critical patent/CN108461723B/en
Publication of CN108461723A publication Critical patent/CN108461723A/en
Application granted granted Critical
Publication of CN108461723B publication Critical patent/CN108461723B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The present invention relates to a kind of silicon based composite materials, include silica lithium compound particle, and the carbon film layer or carbon film and conductive additive being coated on outside silica lithium compound particle composite film；The silica lithium compound particle has nucleocapsid, shell is the lithium silicate compound of densification, lithium silicate compound of the kernel for amount containing lithium less than shell or the silicon oxide compound without lithium, the content of elemental lithium are continuously decreased from shell to kernel, and without sharp interface；The silica lithium compound particle also includes evenly dispersed simple substance nano silicon particles.Protection structure of this silicon based composite material due to the composite film of its carbon film layer or carbon film/conductive additive, lithium silicate compound shell; it can be applied not only to oil system and apply also for water system homogenate system; it is allowed to have both outstanding battery performance and good processing performance, be suitble to commercially use.

Description

A kind of silicon based composite material and preparation method thereof for lithium ion battery
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of silicon based composite material and preparation method thereof.
Background technology
It answers due to the fast development of various portable electronic devices, electric vehicle and energy-storage system in recent years and extensively With the demand of lithium ion battery that is high for energy density, having extended cycle life is increasingly urgent to.Current commercialized lithium ion battery Negative material be mainly graphite, but since theoretical capacity is low (372mAh/g), limit lithium ion battery energy density into One step improves.Since silicium cathode material has the high power capacity advantage that other negative materials can not be equal to, became ground in recent years Heat generating spot, and gradually from laboratory, business application is moved towards in research and development.There are mainly two types of silicium cathode materials, first, elemental silicon and its same carbon The composite material of material；Another kind is silicon oxide compound and its composite material with carbon material.Elemental silicon negative material has very (embedding lithium state is Li to high capacity advantage at room temperature15Si4, theoretical lithium storage content about 3600mAh/g), it is current commercial graphite cathode 10 times or so of materials theory capacity.But there are serious bulk effect, bodies during embedding de- lithium for elemental silicon negative material Product change rate is about 300%, and electrode material dusting and electrode material can be caused to be detached with collector.In addition, due to silicium cathode Material in battery charge and discharge process constantly dilation and lasting rupture, the fresh surfaces produced are exposed to meeting in electrolyte New SEI films are formed, to persistently consume electrolyte, reduce the cycle performance of electrode material.Drawbacks described above seriously limits Its commercial applications.Silicon oxide compound theoretical capacity is about 1700mAh/g, although its capacity is less than elemental silicon negative material, Its expansion rate and cyclical stability have a clear superiority, compared to be more easy to for elemental silicon realize industrial applications.However, silicon aoxidizes Generate the substances such as lithium metasilicate and lithia when closing initial charge of the object in lithium ion battery, lithium ion when electric discharge in the substance It can not deviate from, cause the coulombic efficiency for the first time of battery relatively low (theoretical efficiency is about 70%), it is close to limit full battery energy The promotion of degree.In addition, the ion and electronic conductivity of silicon oxide compound are relatively low, in lithium ion battery first run charge and discharge process De- lithium and embedding lithium reaction and it is insufficient, cause coulombic efficiency in further battery cyclic process relatively low, cycle conservation rate it is not high.Needle To the above problem of silicon oxide compound, scientific research personnel has carried out the improvement of following aspect.
Application publication number is that the Chinese patent literature of CN103840136A and CN104471757A discloses a kind of electric storage means Part silicon systems negative material, electricity storage device electrode, electrical storage device and their manufacturing method.The silicon systems negative material Manufacturing method be that silicon systems material that is absorbable, releasing lithium ion and lithium metal are kneaded mixing there are solvent, Its Patent CN103840136A selections implement heat treatment to form lithium metasilicate, to manufacture pre-doping lithium after mixing mixing Negative material.The mixing of the material needs to carry out under an inert atmosphere, and is related to the use of organic solvent, at discharge Reason or recovery process.The silicon systems negative material is easily reacted or is partly dissolved with water regardless of whether through Overheating Treatment Yu Shui causes the destruction of material structure and is homogenized the unstable of system, therefore it is even to be applied to current lithium electrician industry cathode The water system system generally used is starched, the homogenate system of organic solvent is can be only applied to.Therefore no matter from production process or apply It is all difficult to realize industrialize and be commercialized for process.
It is negative that the Chinese patent literature that application publication number is CN104979524A discloses a kind of non-aqueous electrolyte secondary battery Pole, the negative electrode active material layer formed containing negative electrode active material and adhesive by two kinds or more.Negative electrode active material packet Contain silicon-based active material and active carbon material.The silicon-based active material is carbonated lithium covering by surface layer at least part SiOxIt is formed, it is preferably internal to contain at least one of lithium metasilicate and positive lithium metasilicate.The silicon-based active material passes through Li is mixed SiO by special device with the method for electrochemistryxIn, and form lithium carbonate on surface.This method is complicated for operation, raw It produces less efficient, it is difficult to realize large-scale industrial production.And in the water system homogenization process of actual battery production, the silicon Aqueous slurry can be partially dissolved in by being the lithium carbonate of active material cladding and positive lithium metasilicate, cause slurry pH value to increase, rheological characteristic It can deteriorate, be unfavorable for stabilization and the coating of slurry.The lithium carbonate of the silicon-based active material cladding does not have electro-chemical activity, this The increase of the invalid quality of kind can reduce the specific capacity of material, to reduce the energy density of lithium ion battery.
Authorization Notice No. is that the Chinese patent literature of CN101047234B discloses a kind of silicon-silicon oxide-lithium composite material, Include silicon particle of the size being dispersed therein in 0.5-50nm.The preparation method of the material is included in atmosphere of inert gases It is interior that silica is carried out by mechanical mixture with the lithium metal and/or organo-lithium compound for being used as lithiumation agent by planetary ball mill, Simultaneously during the reaction control ball mill tank in temperature at 40-120 DEG C.In material XRD structure charts shown in the patent The presence of clearly visible positive lithium metasilicate phase.In water system homogenization process, positive lithium metasilicate is water-soluble to cause material self structure It destroys, the problems such as slurry pH is increased, Stability of Slurry deteriorates, therefore not to be suitable for lithium ion battery production field wide for the material The general aqueous homogenate technique used.The preparation method of the material is using lithium metal and/or organo-lithium compound and silica chemical combination The ball milling progress prelithiation reaction in confined space after object directly mixes.The spontaneous progress of the reaction, and typically more acutely, be not easy Its extent of reaction is controlled, if the control of ball grinder cooling condition is bad easily to occur explosion danger, therefore, it is difficult to realize industrialization Safety in production.
Application publication number discloses a kind of silicon based composite material for the Chinese patent literature of CN103400971A, including：Silicon The mixture of particle, silicate and optional carbon, silicate and optional carbon forms blocks, and silicon particle is dispersed in blocks In.Preparation method includes：Silicon particle, silicate and optional carbon are distributed to be formed in absolute ethyl alcohol and/or deionized water and hanged Supernatant liquid is heated and is stirred until flashing to paste；It dries, be ground up, sieved later, be heat-treated in an inert atmosphere, grinding, mistake Sieve obtains silicon based composite material.The silicon particle size (generally higher than 100nm) that the method is selected is much larger than in silicon oxide compound The silicon nanoparticle (being generally less than 50nm) that disproportionated reaction generates, therefore the silicon particle volume in battery charge and discharge process is swollen Swollen/blockage effect is apparent；In addition, the silicon particle dispersibility in the method is also not as good as disproportionated reaction generation in silicon oxide compound Nano-silicon, the non-uniform dispersion of silicon particle also result in the material internal stress distribution unevenness in battery charge and discharge process, to Material granule is caused to rupture；Furthermore the interface stability of silicon particle and lithium metasilicate is not as good as discrimination in silicon oxide compound in the material Elementary silicon/lithium metasilicate the complex changed and generated after prelithiation reaction, more easily leads to material granule in battery charge and discharge process Rupture.In conclusion the cyclical stability of the silicon based composite material is difficult to be guaranteed.
Therefore, existing silicon based anode material is with capacity is low, coulombic efficiency is low, cyclical stability is poor, preparation process is complicated The problems such as dangerous, incompatible with the present aqueous homogenate system generally used, it is difficult to realize the commercialization in lithium ion battery Using being the technical barrier of fields.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of capacity height, coulombs for lithium ion battery It is efficient, have extended cycle life, can be used water system homogenate system silicon based composite material and its can prepare with scale method.
To achieve the above object, technical solution provided by the invention is：
A kind of silicon based composite material includes silica lithium compound particle, and is coated on outside silica lithium compound particle Film layer, the film layer is carbon film/conductive additive composite film that carbon film layer or carbon film layer are formed with conductive additive；It is described It is the lithium silicate compound of densification that silica lithium compound particle, which has nucleocapsid, the shell of nucleocapsid, nucleocapsid Kernel is lithium silicate compound of the amount containing lithium less than shell or silicon oxide compound without lithium, and the content of elemental lithium is from silica lithium The shell of compound particle to kernel continuously decreases, and without sharp interface；The silica lithium compound particle also includes uniform The simple substance nano silicon particles of dispersion.
The median particle diameter of the silica lithium compound particle is scattered between 0.2-20 μm in silica lithium compound particle Simple substance nano silicon particles median particle diameter between 0.1-35nm；Carbon film layer or carbon outside the silica lithium compound particle Film/conductive additive composite film thickness is between 0.001-5 μm；In the silica lithium compound particle, silicon content For 49.9-79.9wt%, oxygen element content 20-50wt%, elemental lithium content is 0.1-20wt%, three kinds of constituent content adductions It is 100%；In the carbon film layer, the ratio between carbon film and silica lithium compound particle weight are 0.01:100-20:100；Described In carbon film/conductive additive composite film, the ratio between carbon film and silica lithium compound particle weight are 0.01:100-20:100, it leads The ratio between electric additive and silica lithium compound particle weight are 0:100-10:100.
The silica lithium compound particle also contains a small amount of doped chemical, and the content of the doped chemical is closed from silica lithiumation The shell of composition granule to kernel continuously decreases, and without sharp interface；The doped chemical be P, F, Mg, Al, Ca, Cu, B, Fe, The combination of one or more of Mn, Zn, Zr, Ti, Sn；In the silica lithium compound particle, silicon content is 49.89-79.89wt%, oxygen element content 20-50wt%, elemental lithium content are 0.1-20wt%, and doped chemical content is 0.01-10%, silicon, oxygen, lithium and doped chemical content adduction be 100%；
The preparation method of above-mentioned silicon based composite material is also disclosed in the present invention, includes the following steps：
(1) silicon oxide compound particle surface is coated into carbon film layer or carbon film/conductive additive composite film, then carried out Broken and sub-sieve；
(2) material obtained by step (1) is uniformly mixed with lithium-containing compound powder；Or it will be obtained by step (1) Material be carried out at the same time uniform mixing with lithium-containing compound powder and dopant；Or the material obtained by step (1) is mixed together After miscellaneous material is first uniformly mixed and carries out heat treatment doping in nonoxidizing atmosphere, then it is equal with the progress of lithium-containing compound powder Even mixing, wherein the dopant is simple substance or compound powder containing doped chemical；
(3) mixing material obtained by step (2) is heated in nonoxidizing atmosphere, make elemental lithium or lithium and mixed Miscellaneous elements diffusion enters silicon oxide compound particle, then carries out broken and sub-sieve, obtains silicon based composite material.
In step (1)：
Silicon and oxygen element stoichiometric ratio in the silicon oxide compound particle are 1:0.5-1:1.5；
The carbon film layer is directly obtained by way of chemical vapor deposition, or by first carrying out carbon matrix precursor cladding again The mode that heat treatment carbonization is carried out in nonoxidizing atmosphere obtains；
The carbon film/conductive additive composite film obtains in the following manner：Have been subjected to chemical vapor deposition progress After the silicon oxide compound particle of carbon film coated is mixed with conductive additive and carbon matrix precursor, then hot place is carried out in nonoxidizing atmosphere Reason carbonization；Or after mixing silicon oxide compound particle with conductive additive and carbon matrix precursor, then carried out in nonoxidizing atmosphere Heat treatment carbonization obtains；
The method for coating of the carbon matrix precursor or carbon matrix precursor and conductive additive using mechanical fusion machine, VC mixing machines, Coat any one in kettle, spray drying, sand mill or high speed dispersor, the solvent that when cladding selects is water, methanol, second Alcohol, isopropanol, n-butanol, ethylene glycol, ether, acetone, N-Methyl pyrrolidone, espeleton, tetrahydrofuran, benzene, toluene, two One or more combinations in toluene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, chloroform；
The carbon matrix precursor is selected from coal tar pitch and petroleum asphalt, polyvinyl alcohol, epoxy resin, polyacrylonitrile, polymethylacrylic acid One or more combinations in methyl esters, glucose, sucrose, polyacrylic acid, polyvinylpyrrolidone；
The conductive additive is Super P, Ketjen black, gas-phase growth of carbon fibre, acetylene black, electrically conductive graphite, carbon nanometer One or more combinations in pipe, graphene；
The heat treatment carbonization device therefor is appointing in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace Meaning is a kind of；
The temperature of the heat treatment carbonization is 500-1200 DEG C, and soaking time is 0.5-24 hours；
The nonoxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium；
The break process is using any one in airslide disintegrating mill, ball mill, turbine type crushing machine.
Any one in the sub-sieve vibrating sieving machine, gas flow sizing machine.
In step (2)：
The lithium-containing compound powder is the reproducibility compound containing lithium；
The dopant is simple substance or chemical combination containing P, F, Mg, Al, Ca, Cu, B, Fe, Mn, Zn, Zr, Ti, Sn element One or more of combinations of object powder；
The maximum particle diameter of the lithium-containing compound powder and the dopant is less than or equal to 60 μm；
The grinding mode of the lithium-containing compound powder and the dopant is mortar grinder, ball mill, air-flow crushing Any one in machine, turbine type crushing machine.
The mixed method is stirred using high speed dispersor, high-speed stirred mill, ball mill, cone-type mixer, mixing screw Mix any one in formula mixing machine or VC mixing machines.
In step (3)：
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 400-950 DEG C, and soaking time is 0.1-12 hours, and heating rate is more than 5 DEG C every point Clock, it is 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.
The break process is using any one in airslide disintegrating mill, ball mill, turbine type crushing machine.
Any one in the sub-sieve vibrating sieving machine, gas flow sizing machine.
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 prior art, the present invention having the following advantages that：
1. the nano silicon particles inside silica lithium compound particle are what disproportionated reaction " from bottom to top " generated, size is far small In the silicon particle that other " from top to bottom " breaking methods obtain, therefore bulk effect during removal lithium embedded is small.Silica lithiumation Nano silicon particles inside polymer beads are evenly dispersed and are fixed in lithium silicate compound or silicon oxide compound matrix, Described matrix can effectively inhibit and buffer the expansion of nano silicon particles, and silicon particle is prevented gradually to melt simultaneously in charge and discharge process At larger sized particle, prevent from melting and after large scale silicon particle cause bigger expansion and part silicon materials failure.
2. compared with traditional silicon oxide compound negative material, lithium, oxygen and element silicon inside silica lithium compound particle In the form of lithium silicate compound exist, oxygen element therein will not be continuously formed in lithium intercalation lithium metasilicate or The compounds such as lithia, therefore the irreversible loss of lithium ion when greatly reducing its first charge-discharge caused by oxygen element, Namely improve for the first time coulombic efficiency of the material in lithium ion battery.
3. a large amount of lithium atoms of pre- insertion inside the silica lithium compound particle in the present invention, with traditional silicon oxide compound Material compares in the case of same de- lithium capacity, the former lithium ion of the required insertion in battery first run charge and discharge is more compared with the latter It is few, therefore the expansion rate of particle is lower, to which the expansion rate of battery pole piece and battery is lower, is conducive to negative material particle, bears The stable structure of pole pole piece and battery is conducive to the cyclical stability of battery.
4. in the material preparation method of the present invention, to lithium-containing compound and doped chemical simple substance or compound particle maximum grain The control of diameter is mixed with the uniform of silicon oxide compound powder, and to subsequent heat treatment heating rate, temperature and time it is accurate Control is conducive to lithium and doped chemical and silicon oxide compound homogeneous reaction, generates uniformly and outside fine and close silicate compound Shell.
5. in water system homogenization process, the silicate compound shell of silica lithium compound particle outer layer densification can incite somebody to action Internal nano silicon particles completely cut off completely with extraneous aqueous slurry, avoid nano silicon particles and contact generation air-generating reaction with water and make The loss of Viability silicon materials；Fine and close silicate compound shell water-tolerant has the pH raisings effect of aqueous slurry Limit, do not interfere with the rheological equationm of state and stability of slurry, therefore effectively prevent in coating process because aerogenesis, slurry rheological property and The pole pieces quality problems such as uneven, the bonding difference of pole piece pin hole, pit, surface density caused by stability deteriorates.
6. in lithium ion battery, the silicate compound shell of silica lithium compound particle outer layer densification, energy will be interior The nano silicon particles in portion completely cut off with extraneous electrolyte completely completely, and surface energy forms more stable SEI films, and material is greatly improved Expect coulombic efficiency and capacity stability in battery charging and discharging cyclic process.
7. for the material being co-doped with elemental lithium using doped chemical, a small amount of of silica lithium compound particle outer layer enrichment mixes Miscellaneous element can make its surface texture more water-fast；Surface can also be made to be formed in lithium ion battery and more stablize densification SEI films.
8. the silicon oxide compound particle that pair outer surface is coated with the composite film of carbon film or carbon film and conductive additive carries out When lithium reaction is mixed in heat treatment, elemental lithium when diffusing into silicon oxide compound particle can by the certain inhibition of carbon film, because This is more easy to form elemental lithium compared to the lithium silicate compound shell that kernel is more enriched in outer layer.
9. the composite film of carbon film or carbon film and conductive additive is coated with outside silicon based composite material particle, it can be with one Determine to avoid being in direct contact for silica lithium compound and aqueous slurry in degree, reduces its negative effect to slurry.In addition, carbon film Electrolyte and silica lithium compound particle can also be avoided to be in direct contact to a certain extent, relatively stable SEI films can be formed, carried High interface stability improves the coulombic efficiency and cyclical stability of material.
10. being coated with the composite film of carbon film or carbon film and conductive additive, Ke Yiyou outside silicon based composite material particle Effect improves the conductivity of particle, reduces in cathode pole piece between particle, the contact resistance of cathode pole piece and collector, to improve The removal lithium embedded efficiency of material reduces the polarization of lithium ion battery and promotes its cyclical stability.
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, the low electrochemical properties of expansion rate.The lithium ion battery of the preparation of the silicon based composite material has volume The low characteristic of energy density height, good cycling stability, expansion.The preparation method of the silicon based composite material is simple, at low cost, again Renaturation is good, and required equipment is simple, can large-scale industrial production, and the water system cathode that industrial quarters generally uses can be directly applied to It is homogenized process system, can really realize the scale application containing silicium cathode in field of lithium ion battery.
Description of the drawings
Fig. 1 is the structural schematic diagram of the silicon based composite material of the present invention.
Fig. 2 is 20000 times of stereoscan photographs of silicon based composite material prepared by embodiment 1.
Fig. 3 is the cycle performance figure of the full battery containing silicium cathode prepared by embodiment 1.
Fig. 4 is 10000 times stereoscan photographs of the silicon based composite material of the preparation of embodiment 2 after soaking 72 hours.
Fig. 5 is X ray diffracting spectrum of the silicon based composite material of the preparation of embodiment 2 after soaking 72 hours.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
A kind of silicon based composite material provided by the invention includes silica lithium compound particle and its surface coated carbon film The composite film of layer or carbon film and conductive additive.As shown in Figure 1, the shell 1 of silica lithium compound particle is fine and close silicic acid Lithium based compound, kernel 2 are silicon oxide compound or lithium silicate compound, and simple substance nano silicon particles 3 are dispersed in silica lithium The content of the inside of compound particle, elemental lithium is continuously decreased from shell to kernel, no sharp interface.Carbon film layer 4 or carbon film and The composite film of conductive additive 5 is coated on silica lithium compound particle surface.
Embodiment 1
By silicon oxide compound particle that 1000g median particle diameters are 6 μm, (silicone atom ratio is 1:1), 65g low temperature pitch powder End, 10g Ketjen blacks powder cladding kettle in dry mixed it is uniform after, while stirring be added 2000g dimethylformamides, will mix Powder is uniformly dispersed in dimethylformamide.Then heating cladding kettle to 140 DEG C and keeps constant temperature stirring 3 hours, finally again 160 DEG C and constant temperature are heated to until dimethylformamide is evaporated, obtains the silica chemical combination that coal tar pitch and Ketjen black coat jointly Object material.Above-mentioned material is heated to 900 DEG C under nitrogen atmosphere and keeps making coal tar pitch be carbonized in 3 hours, while silica chemical combination Disproportionated reaction occurs for object.By the material fragmentation obtained after cooling and 500 mesh screens are crossed, obtain carbon film/Ketjen black composite film packet The silicon oxide compound powder covered.
In drying room of the relative humidity less than 30%, 600 are crossed after lithium hydride coarse powder being crushed using planetary ball mill Mesh screen, obtained lithium hydride fine powder, maximum particle size are approximately equal to 23 μm.Hydrogenation magnesium powder is made using same method. The lithium hydride fine powder 50g after screening, hydrogenation magnesium powder 5g are taken, the silica chemical combination with above-mentioned carbon film/Ketjen black composite film cladding Object powder 500g is mixed 20 minutes in VC mixing machine high speeds.Above-mentioned mixed-powder is put into tube furnace, under argon atmosphere It carries out mixing lithium, doping heat treatment, be kept for 60 minutes after being warming up to 750 DEG C with the heating rate of 10 DEG C/min, it will after natural cooling Material takes out from tube furnace and crosses 500 mesh screens, obtains final silicon based composite material product.Wherein, silica lithium magnesium granules contain There are element silicon about 58wt%, oxygen element about 33wt%, elemental lithium about 8wt%, magnesium elements about 1wt%；Carbon film layer and conductive addition Agent respectively may be about 4.1 with the weight ratios of silica lithium magnesium granules:100 and 0.9:100.By X-ray diffraction analysis, silicon at this time The silicon nanocrystal particle size of oxygen lithium magnesium granules inner homogeneous dispersion is about 7nm.
Fig. 2 show the electron scanning micrograph of the final silicon based composite material product of embodiment 1, amplification factor 20000 times, it can clearly be seen that carbon film and Ketjen black are uniformly wrapped on silica lithium magnesium granules surface.
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 It is homogenized under property system, is coated with, dries, rolling, obtain siliceous cathode pole piece.
Half-cell is assessed：Above-mentioned siliceous cathode pole piece and diaphragm, lithium piece, stainless steel gasket are stacked successively 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 of 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 447mAh/ G, first charge-discharge efficiency (de- lithium stopping potential 0.8V) 91.6%.
Full battery is assessed：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. of Shenzhen Capacity, average voltage of the full battery at 0.2C, and charge and discharge cycles 500 times obtain capacity retention ratio number under 0.7C multiplying powers According to.Thus the volume energy density for obtaining full battery is 769Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 85.3%.Fig. 3 is the cycle performance figure of the full battery containing silicium cathode prepared by embodiment 1.
Embodiment 2
Compared to embodiment 1, embodiment 2 is without using conductive additive Ketjen black and dopant magnesium hydride, other materials Expect that preparation process and evaluation method are same as Example 1.The silicon nanocrystal of gained silicon substrate composite particles inner homogeneous dispersion Size is about 6nm.The final de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 448mAh/g, first charge-discharge Efficiency 91.1%.The volume energy density for measuring full battery reaches 769Wh/L, the capacity retention ratio after 500 charge and discharge cycles It is 84.3%.
The silicon based composite material product that Fig. 4 show embodiment 2 impregnates the scanning electron microscope after 72 hours in water Photo, 10000 times of amplification factor.Before its surface topography is compared to immersion, any variation does not occur.Fig. 5 show embodiment 2 Silicon based composite material product impregnate in water 72 hours before and after X ray diffracting spectrum comparison, it is seen that do not have on crystal structure Any variation.Meanwhile also draining water gathering of gas law being used to impregnate 72 hours mistakes in water for the silicon based composite material product of embodiment 2 Gas production caused by may reacting with water in journey measures, and is not as a result collected into any aerogenesis.Above 3 points prove The materials water-resistant is splendid, therefore can be resistant to usually only needs 6-8 hours cathode water systems to be homogenized coating process completely.And In the homogenate coating process of embodiment 2, thinning any slurry, caking and aerogenesis are not observed yet, and coated face density is uneven, applies The bad problem such as cloth shrinkage cavity.
Embodiment 3
Compared to embodiment 1, embodiment 3 uses sucrose instead and coats presoma as carbon film layer, and Super P are added as conductive Agent, copper is as doped chemical.Specific preparation method be by 1000g silicon oxide compounds particle, 10g Super P powder, Slurry is carried out spray drying treatment by 203g copper citrates and 50g sucrose after the dispersion of 5000g deionized water high speeds, then will Obtained powder under nitrogen atmosphere, 900 DEG C heating 5 hours after be crushed and cross 500 mesh screens.Carbon film layer obtained above/ The Copper-cladding Aluminum Bar silicon oxide compound particle that Super P composite films coat altogether mix lithium technique and evaluation method with 1 phase of embodiment Together.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 8nm.Final half electricity measured containing silicium cathode The de- lithium specific capacity reversible for the first time in pond is 437mAh/g, first charge-discharge efficiency 92.1%.The volume energy for measuring full battery is close Degree reaches 767Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 85.0%.
Embodiment 4
Compared to embodiment 1, the silicon oxide compound particles coat carbon technology in embodiment 4 uses chemical vapor deposition Method carries out completion in 3 hours as carbon matrix precursor using methane at 900 DEG C, does not add conductive additive additionally.In addition, taking 55g boron Lithium hydride fine powder replaces lithium hydride and hydrogenation magnesium powder to be used as and mix lithium, dopant.Other materials preparation process and evaluation method It is same as Example 1.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 11nm.Finally measure The de- lithium specific capacity reversible for the first time of half-cell containing silicium cathode is 436mAh/g, first charge-discharge efficiency 91.9%.Measure full electricity The volume energy density in pond reaches 764Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 83.7%.
Embodiment 5
Compared to embodiment 2, embodiment 5 carries out asphalt using the VC mixing machines of hot type to silicon oxide compound powder Cladding, used the lithium hydride fine powder 50g of 500 mesh screens as lithium compound is mixed, the temperature for mixing lithium heat treatment rises to 820 DEG C, other materials preparation process and evaluation method are same as Example 2.The silicon of gained silicon substrate composite particles inner homogeneous dispersion Nanocrystalline grain size is about 10nm.The final de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 443mAh/g, First charge-discharge efficiency 92.7%.The volume energy density for measuring full battery reaches 774Wh/L, after 500 charge and discharge cycles Capacity retention ratio is 84.0%.
Embodiment 6
Compared to embodiment 1, pitch and Ketjen black coat the heat treatment condition after silicon oxide compound particle in embodiment 6 It is changed at 1000 DEG C 2 hours, the 100g lithium aluminium hydride reduction fine powders replacement lithium hydride of 500 mesh screens and magnesium hydride was used to be used as and mix Lithium, dopant.Mix lithium, doping heat treatment temperature is improved to 770 DEG C.Other materials preparation process and evaluation method with implementation Example 1 is identical.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 19nm.Finally measure containing silicium cathode Half-cell de- lithium specific capacity reversible for the first time be 432mAh/g, first charge-discharge efficiency 92.2%.Measure the volume of full battery Energy density reaches 764Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 81.6%.
Embodiment 7
Compared to embodiment 5,7 petrochina asphalt powder additive amount of embodiment increases to 200g, and lithium hydride fine powder dosage increases Add to 75g, mix lithium heat treatment time and extend to 120 minutes, other materials preparation process and evaluation method with 5 phase of embodiment Together.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 14nm.Final half measured containing silicium cathode The de- lithium specific capacity reversible for the first time of battery is 440mAh/g, first charge-discharge efficiency 90.8%.Measure the volume energy of full battery Density reaches 761Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 83.5%.
Embodiment 8
It is 3 μm of silicon oxide compound powder, 150g polyvinyl alcohol and leading containing 10g graphenes to take 1000g median particle diameters Plasma-based material carries out spray drying treatment after three is uniformly dispersed by sand mill with 4000g deionized waters.By above-mentioned gained powder End is heated to 700 DEG C and is kept for 2 hours under nitrogen atmosphere, is crushed after cooling and crosses 500 mesh sieve, carbon film/graphene of gained Under this heat treatment temperature disproportionated reaction does not occur for the silicon oxide compound powder of composite film cladding.It is mixed with lithium hydride fine powder Lithium heat treatment heating rate of mixing after closing uniformly is improved to 20 DEG C/min.Other preparation processes and evaluation of material method with implementation Example 5 is identical.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 12nm.Finally measure containing silicium cathode Half-cell de- lithium specific capacity reversible for the first time be 441mAh/g, first charge-discharge efficiency 92.4%.Measure the volume of full battery Energy density reaches 772Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 82.9%.
Embodiment 9
Compared to embodiment 5, using 65g coal tar pitch as carbon matrix precursor in embodiment 9,10g Ketjen blacks are added as conductive Agent carries out liquid phase coating using cladding kettle to silicon oxide compound powder.Silica chemical combination after pitch/Ketjen black composite film cladding Object powder is heat-treated 2 hours at 1150 DEG C, and other materials preparation process and evaluation method are same as Example 5.Gained silicon The silicon nanocrystal particle size of base composite particles inner homogeneous dispersion is about 10nm.Finally measure the half-cell containing silicium cathode for the first time Reversible de- lithium specific capacity is 434mAh/g, first charge-discharge efficiency 92.8%.The volume energy density for measuring full battery reaches 767Wh/L, the capacity retention ratio after 500 charge and discharge cycles are 82.7%.
Embodiment 10
Compared to embodiment 5, the lithium hydride fine powder of 600 mesh screens was used in embodiment 10, and usage amount is reduced to In addition 25g additionally adds 5g and crosses the lithium fluoride fine powders of 600 mesh screens as dopant, subsequent mixes lithium, doping heat treatment Condition is to be heated 480 minutes at 450 DEG C.Other materials preparation process and evaluation method are same as Example 5.Gained silicon substrate is multiple The silicon nanocrystal particle size for closing the dispersion of particle inner homogeneous is about 5nm.Finally measure the reversible for the first time of the half-cell containing silicium cathode De- lithium specific capacity is 463mAh/g, first charge-discharge efficiency 87.7%.The volume energy density for measuring full battery reaches 762Wh/ L, the capacity retention ratio after 500 charge and discharge cycles are 85.1%.
Embodiment 11
Compared to embodiment 5, the silicon oxide compound powder heat treatment Carbonization Conditions of 11 petrochina pitch-coating of embodiment are Constant temperature 2 hours at 1050 DEG C, lithium hydride fine powder usage amount are reduced to 10g, mix lithium heat treatment temperature and are increased to 930 DEG C, other materials Expect that preparation process and evaluation method are same as Example 5.The silicon nanocrystal of gained silicon substrate composite particles inner homogeneous dispersion Size is about 26nm.The final de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 448mAh/g, for the first time charge and discharge Electrical efficiency 89.9%.The volume energy density for measuring full battery reaches 764Wh/L, and the capacity after 500 charge and discharge cycles is kept Rate is 80.8%.
Embodiment 12
Take 1000g silicon oxide compound powder, 150g polyvinyl alcohol, the electrocondution slurry containing 10g multi-walled carbon nanotubes, 10g Amphiphilic Ketjen black powder carries out spray drying treatment after four are uniformly dispersed by sand mill with 4000g deionized waters, obtains The silicon oxide compound material coated jointly to polyvinyl alcohol, multi-walled carbon nanotube and Ketjen black.By above-mentioned material in nitrogen atmosphere Under be heated to 900 DEG C and kept for 2 hours, obtained material powder be crushed after cooling and crosses 500 mesh and is sieved.It mixes and is hydrogenated in lithium technique The usage amount of lithium fine powder is improved to 65g.Other materials preparation process and evaluation method are same as Example 5.Gained silicon substrate is multiple The silicon nanocrystal particle size for closing the dispersion of particle inner homogeneous is about 13nm.Finally measure the reversible for the first time of the half-cell containing silicium cathode De- lithium specific capacity is 447mAh/g, first charge-discharge efficiency 91.1%.The volume energy density for measuring full battery reaches 766Wh/ L, the capacity retention ratio after 500 charge and discharge cycles are 83.7%.
Embodiment 13
It is 1 μm of silicon oxide compound powder, 200g sucrose, the slurry containing 1g single-walled carbon nanotubes to take 1000g median particle diameters Material, is spray-dried after three is uniformly dispersed by sand mill with 4000g deionized waters, obtains sucrose, single Manage the silicon oxide compound material coated jointly.Above-mentioned material is heated to 900 DEG C under nitrogen atmosphere and is kept for 2 hours, it is cooling Obtained material powder is crushed afterwards and crosses 500 mesh sieve.It mixes in lithium technique, used the lithium hydride fine powder 25g of 600 mesh screens, The heating rate for mixing lithium heat treatment is improved to 20 DEG C/min, and soaking time is shorten to 10 minutes.It other materials preparation process and comments Valence method is same as Example 5.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 9nm.Most The de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode eventually is 447mAh/g, first charge-discharge efficiency 90.1%.It surveys The volume energy density for obtaining full battery reaches 765Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 82.1%.
Embodiment 14
Compared to embodiment 2, the silicon oxide compound particles coat carbon technology in embodiment 14 uses chemical vapor deposition Area method carries out completion in 2 hours as carbon matrix precursor using ethylene at 1000 DEG C, does not add conductive additive additionally.It mixes at lithium heat Reason temperature is reduced to 600 DEG C.Other materials preparation process and evaluation method are same as Example 2.Gained silicon substrate composite particles The silicon nanocrystal particle size of inner homogeneous dispersion is about 5nm.The final de- lithium ratio reversible for the first time for measuring the half-cell containing silicium cathode Capacity is 457mAh/g, first charge-discharge efficiency 89.4%.The volume energy density for measuring full battery reaches 763Wh/L, 500 times Capacity retention ratio after charge and discharge cycles is 85.7%.
Embodiment 15
Compared to embodiment 14, the calcium hydride for additionally adding 600 mesh screens in embodiment 15 in mixing lithium technique is thin For powder 15g as dopant, other materials preparation process and evaluation method are identical as embodiment 14.Gained silicon substrate composite particles The silicon nanocrystal particle size of inner homogeneous dispersion is about 6nm.The final de- lithium ratio reversible for the first time for measuring the half-cell containing silicium cathode Capacity is 449mAh/g, first charge-discharge efficiency 90.1%.The volume energy density for measuring full battery reaches 765Wh/L, 500 times Capacity retention ratio after charge and discharge cycles is 86.0%.
Comparative example 1
Technical process similar embodiment 2, difference lies in do not use lithium hydride fine powder to be used as to mix lithium substance, therefore product For the silicon oxide compound particle of the carbon film coated without containing elemental lithium.The silicon nanometer of gained silicon substrate composite particles inner homogeneous dispersion Crystallite dimension is about 4nm.Half-cell and full battery appraisal procedure measure for the first time may be used for the half-cell containing silicium cathode with embodiment 2 Inverse de- lithium specific capacity is 463mAh/g, first charge-discharge efficiency 84.5%.The volume energy density for measuring full battery reaches 745Wh/L, the capacity retention ratio after 500 charge and discharge cycles are 84.2%.Due to not containing lithium member in the material of comparative example 1 Element, the negative material charge for the first time in lithium ion battery embedding lithium when can form lithium silicate compound or lithia, make At higher lithium ion irreversible loss, to cause first charge-discharge efficiency low, in turn result in the energy density of full battery compared with It is low.
Comparative example 2
Technical process similar embodiment 2, difference lies in silicon oxide compound powder without pitch-coating processing, is only disproportionated Reaction heat treatment.The silicon nanocrystal particle size of the final silicon substrate composite particles inner homogeneous dispersion of gained is about 7nm.Half-cell and For full battery appraisal procedure with embodiment 2, the de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode is 430mAh/g, first Secondary efficiency for charge-discharge 89.2%.The volume energy density for measuring the full battery containing silicium cathode is 740Wh/L, and 500 charge and discharge follow Capacity retention ratio after ring is 78.3%.Material in comparative example 2 does not have the packet of carbon film layer or carbon film/conductive agent composite film It covers, therefore elemental lithium is more easy to diffuse into inside silicon oxide compound particle and is not easy to be enriched with shape in particle outer layer during mixing lithium At fine and close silicate compound shell.And without carbon film layer or the silica lithium compound particle of composite film protection in water system It is more unstable in homogenization process.It is caused to lead in addition, material lacks carbon film layer or the cladding of carbon film/conductive agent composite film Electrically poor, it is low that the polarization of the battery in charge and discharge process will also result in efficiency for charge-discharge, and capacity is low and to recycle conservation rate low etc. Problem.Finally, lack carbon film layer or carbon film/conductive agent composite film cladding cathode particle surface be not easy to be formed it is stable SEI, therefore it is poor to recycle conservation rate.
Comparative example 3
Technical process similar embodiment 2, difference lies in the usage amounts of lithium hydride to increase to 150g.Compound of gained silicon substrate The evenly dispersed silicon nanocrystal particle size in intragranular portion is about 13nm.Half-cell and full battery appraisal procedure measure and contain with embodiment 2 The de- lithium specific capacity reversible for the first time of the half-cell of silicium cathode is 407mAh/g, first charge-discharge efficiency 84.0%.It measures siliceous negative The volume energy density of the full battery of pole is 652Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 70.3%.Hydrogenation The excessively high usage amount of lithium makes to form a large amount of positive lithium metasilicate or even lithia in product.The positive lithium metasilicate in water system homogenization process With lithia can be dissolved in water or reacted with water, to make slurry become strong basicity, while causing the broken of silica lithium grain structure It is bad.State is extremely unstable under alkaline condition for slurry, such as the problems such as conductive agent is reunited, and thickener and bonding agent fail.In addition, knot Silicon nanocrystal in the silica lithium particle that structure is destroyed, which is exposed in alkaline solution, can occur violent reaction, produce in the slurry Raw a large amount of bubbles, influence slurry coating quality, cause a large amount of pits and pin hole.Problem above has eventually led to the capacity of battery Low, efficiency is low, and energy density is low and recycles the shortcomings such as conservation rate difference.
Comparative example 4
Technical process similar embodiment 5, difference lies in mixing in lithium heat treatment process, heating rate is reduced to 5 DEG C/min, 820 DEG C of constant temperature time extends to 1440 minutes.The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about For 15nm.Half-cell and full battery appraisal procedure measure the de- lithium specific volume reversible for the first time of the half-cell containing silicium cathode with embodiment 5 Amount is 420mAh/g, first charge-discharge efficiency 89.1%.The volume energy density for measuring the full battery containing silicium cathode is 739Wh/ L, the capacity retention ratio after 500 charge and discharge cycles are 75.9%.In comparative example 4, lower heating rate and long lithium is mixed Heat treatment time causes lithium ion to have time enough to be spread in entire silicon oxide compound particle uniformly, and the lithium metasilicate formed Based compound matrix crystalline quality is excessively high, and growth is excessively fine and close, reduce entire lithium silicate compound particle lithium ion and Electron mobility, so as to cause the active degradation of material electrochemical.
Comparative example 5
Technical process similar embodiment 5, difference lies in use lithium carbonate to substitute lithium hydride and be used as to mix lithium compound.Gained The silicon nanocrystal particle size of silicon substrate composite particles inner homogeneous dispersion is about 5nm.Half-cell and full battery appraisal procedure are the same as implementation Example 5, the de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode are 415mAh/g, first charge-discharge efficiency 87.2%. The volume energy density for measuring the full battery containing silicium cathode is 688Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 76.3%.The lithium carbonate reactivity used in comparative example 5 is relatively low, to silicon oxide compound to mix lithium less efficient, without shape At enough lithium silicate compounds.In addition, lithium carbonate mixes lithium reaction without being used in image of Buddha embodiment with silicon oxide compound Reproducibility lithium compound it is the same can restore elemental silicon, to cause electro-chemical activity silicone content less, the ratio of material Capacity is relatively low.Finally, the remaining lithium carbonate for failing to react with silicon oxide compound can be dissolved in slurry in alkalinity in homogenization process, make At slurry state deteriorating, coating quality is deteriorated, and influences the chemical property of final full battery.
Comparative example 6
Technical process similar embodiment 5, difference lies in the temperature for mixing lithium heat treatment to improve to 980 DEG C.Gained silicon substrate is multiple The silicon nanocrystal particle size for closing the dispersion of particle inner homogeneous is about 36nm.Half-cell and full battery appraisal procedure are surveyed with embodiment 5 The de- lithium specific capacity reversible for the first time that the half-cell of silicium cathode must be contained is 407mAh/g, first charge-discharge efficiency 89.1%.It measures and contains The volume energy density of the full battery of silicium cathode is 731Wh/L, and the capacity retention ratio after 500 charge and discharge cycles is 53.2%. It is excessively high in comparative example 6 to mix lithium sintering temperature to cause Si nanocrystallite evenly dispersed in silicon substrate composite particles to grow to excessive Size, so as to cause material, volume expansion and contraction are excessive in charge and discharge process, and particle, which constantly ruptures, forms new interface To constantly be concatenated to form SEI and consume lithium ion；The excessive expansion of particle and contraction can also destroy the electricity of itself and neighboring particles The electrical contact for learning contact or even pole piece and collector, to cause the circulation volume conservation rate of battery to decay.
Comparative example 7
Technical process similar embodiment 14, difference lies in lithium hydride coarse powder to be handled without ball milling and sieving, only in mortar It is mixed with the silicon oxide compound powder of carbon film coated after interior grinding, it is 5 DEG C/min to mix the heating rate in lithium heat treatment process. The silicon nanocrystal particle size of gained silicon substrate composite particles inner homogeneous dispersion is about 6nm.Half-cell and full battery appraisal procedure are same Embodiment 14, the de- lithium specific capacity reversible for the first time for measuring the half-cell containing silicium cathode are 436mAh/g, first charge-discharge efficiency 87.5%.The volume energy density for measuring the full battery containing silicium cathode is 705Wh/L, and the capacity after 500 charge and discharge cycles is protected Holdup is 79.1%.For lithium hydride powder in comparative example 7 without size controlling, there are a large amount of grain sizes to be much larger than silicon oxide compound The lithium hydride particle of particle.The excessive lithium hydride particle of more grain size can cause surrounding silicon oxide compound particle to mix lithium amount mistake Height, so that form positive lithium metasilicate or even lithia.Lower heating rate also can make lithium ion diffuse into silicon oxide compound particle Inside, obtained silica lithium compound particle elements are evenly distributed, not fine and close water-fast shell.The material is even in water system It causes slurry in alkalinity during slurry, causes slurry form unstable.The material also reacts with aqueous slurry production simultaneously Raw more bubble causes the loss of active silicon materials and coating quality to deteriorate.The above problems have eventually led to full battery The deterioration of chemical property.
Embodiment electrochemical data summarizes：
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 above real Apply any simple modification, equivalent replacement and improvement etc. made by example, still fall within technical solution of the present invention protection domain it It is interior.

Claims (10)

1. a kind of silicon based composite material, it is characterised in that：Include silica lithium compound particle, and is coated on the conjunction of silica lithiumation Film layer outside composition granule, carbon film/conductive additive that the film layer, which is carbon film layer or carbon film layer, to be formed with conductive additive are compound Film layer；It is the lithium silicate compound of densification, core that the silica lithium compound particle, which has nucleocapsid, the shell of nucleocapsid, The kernel of shell structure is lithium silicate compound of the amount containing lithium less than shell or the silicon oxide compound without lithium, the content of elemental lithium It is continuously decreased from shell to the kernel of silica lithium compound particle, and without sharp interface；The silica lithium compound particle also wraps Contain evenly dispersed simple substance nano silicon particles.
2. silicon based composite material according to claim 1, it is characterised in that：The intermediate value grain of the silica lithium compound particle Diameter is scattered in the median particle diameter of the simple substance nano silicon particles in silica lithium compound particle in 0.1-35nm between 0.2-20 μm Between；Carbon film layer or carbon film/conductive additive composite film thickness outside the silica lithium compound particle is at 0.001-5 μm Between；In the silica lithium compound particle, silicon content 49.9-79.9wt%, oxygen element content 20- 50wt%, elemental lithium content are 0.1-20wt%, and three kinds of constituent content adductions are 100%；In the carbon film layer, carbon film and silicon The ratio between oxygen lithium compound particle weight is 0.01:100-20:100；In the carbon film/conductive additive composite film, carbon film It is 0.01 with the ratio between silica lithium compound particle weight:100-20:100, conductive additive and silica lithium compound particle weight The ratio between be 0:100-10:100.
3. silicon based composite material according to claim 1, it is characterised in that：The silica lithium compound particle also contains few Doped chemical is measured, the content of the doped chemical is continuously decreased from shell to the kernel of silica lithium compound particle, and without apparent Interface；The doped chemical is the combination of one or more of P, F, Mg, Al, Ca, Cu, B, Fe, Mn, Zn, Zr, Ti, Sn； In the silica lithium compound particle, silicon content 49.89-79.89wt%, oxygen element content 20-50wt%, lithium Constituent content is 0.1-20wt%, and doped chemical content is 0.01-10%, silicon, oxygen, lithium and doped chemical content adduction be 100%.
4. the preparation method of any one of the claim 1-3 silicon based composite materials, it is characterised in that：Include the following steps：
(1) silicon oxide compound particle surface is coated into carbon film layer or carbon film/conductive additive composite film, is then crushed And sub-sieve；
(2) material obtained by step (1) is uniformly mixed with lithium-containing compound powder；Or by the material obtained by step (1) Material is carried out at the same time uniform mixing with lithium-containing compound powder and dopant；Or by the same dopant of material obtained by step (1) After matter is first uniformly mixed and carries out heat treatment doping in nonoxidizing atmosphere, then uniformly mixed with lithium-containing compound powder It closes, wherein the dopant is simple substance or compound powder containing doped chemical；
(3) mixing material obtained by step (2) is heated in nonoxidizing atmosphere, makes elemental lithium or lithium and doping member Element diffuses into silicon oxide compound particle, then carries out broken and sub-sieve, obtains silicon based composite material.
5. the preparation method of silicon based composite material as claimed in claim 4, which is characterized in that in step (1)：
The stoichiometric ratio of silicon and oxygen element in the silicon oxide compound particle is 1:0.5-1:1.5；
The carbon film layer is directly obtained by way of chemical vapor deposition, or by first carrying out carbon matrix precursor cladding again non- The mode that heat treatment carbonization is carried out in oxidizing atmosphere obtains；
The carbon film/conductive additive composite film obtains in the following manner：It has been subjected to chemical vapor deposition and carries out carbon film packet After the silicon oxide compound particle covered is mixed with conductive additive and carbon matrix precursor, then heat treated carbon is carried out in nonoxidizing atmosphere Change；Or after mixing silicon oxide compound particle with conductive additive and carbon matrix precursor, then hot place is carried out in nonoxidizing atmosphere Reason carbonization obtains；
The method for coating of the carbon matrix precursor or carbon matrix precursor and conductive additive is using mechanical fusion machine, VC mixing machines, cladding Any one in kettle, spray drying, sand mill or high speed dispersor, the solvent that when cladding selects is water, methanol, ethyl alcohol, different Propyl alcohol, n-butanol, ethylene glycol, ether, acetone, N-Methyl pyrrolidone, espeleton, tetrahydrofuran, benzene,toluene,xylene, One or more combinations in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, chloroform；
The carbon matrix precursor is selected from coal tar pitch and petroleum asphalt, polyvinyl alcohol, epoxy resin, polyacrylonitrile, poly-methyl methacrylate One or more combinations in ester, glucose, sucrose, polyacrylic acid, polyvinylpyrrolidone；
The conductive additive is Super P, Ketjen black, gas-phase growth of carbon fibre, acetylene black, electrically conductive graphite, carbon nanotube, stone One or more combinations in black alkene；
The heat treatment carbonization 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 carbonization is 500-1200 DEG C, and soaking time is 0.5-24 hours；
The nonoxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium；
The break process is using any one in airslide disintegrating mill, ball mill, turbine type crushing machine.
Any one in the sub-sieve vibrating sieving machine, gas flow sizing machine.
6. the preparation method of silicon based composite material as claimed in claim 4, which is characterized in that in step (2)：
The lithium-containing compound powder is the reproducibility compound containing lithium；
The dopant is simple substance or compound powder containing P, F, Mg, Al, Ca, Cu, B, Fe, Mn, Zn, Zr, Ti, Sn element One or more of combinations at end；
The maximum particle diameter of the lithium-containing compound powder and the dopant is less than or equal to 60 μm；
The grinding mode of the lithium-containing compound powder and the dopant is mortar grinder, ball mill, airslide disintegrating mill, whirlpool Any one in wheeled pulverizer.
The mixed method is using high speed dispersor, high-speed stirred mill, ball mill, cone-type mixer, mixing screw, stirring-type Any one in mixing machine or VC mixing machines.
7. the preparation method of silicon based composite material as claimed in claim 4, which is characterized in that in step (3)：
The heat treatment device therefor is any one in rotary furnace, roller kilns, pushed bat kiln, atmosphere batch-type furnace or tube furnace.
The temperature of the heat treatment is 400-950 DEG C, and soaking time is 0.1-12 hours, and heating rate is per minute more than 5 DEG C, small It is per minute in 100 DEG C.
The non-oxidizing atmosphere is provided by following at least one gases：Nitrogen, argon gas, hydrogen or helium.
The break process is using any one in airslide disintegrating mill, ball mill, turbine type crushing machine.
Any one in the sub-sieve vibrating sieving machine, gas flow sizing machine.
8. a kind of lithium ion battery negative material, it is characterised in that：It include the silicon substrate composite wood of any one of claims 1 to 3 The lithium ion battery negative material of material.
9. a kind of negative electrode of lithium ion battery, it is characterised in that：It is prepared using lithium ion battery negative material described in claim 8 Negative electrode of lithium ion battery.
10. a kind of lithium ion battery, it is characterised in that：Using described in claim 9 negative electrode of lithium ion battery prepare lithium from Sub- battery.
CN201810140725.9A 2018-02-11 2018-02-11 Silicon-based composite material for lithium ion battery and preparation method thereof Active CN108461723B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810140725.9A CN108461723B (en) 2018-02-11 2018-02-11 Silicon-based composite material for lithium ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810140725.9A CN108461723B (en) 2018-02-11 2018-02-11 Silicon-based composite material for lithium ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108461723A true CN108461723A (en) 2018-08-28
CN108461723B CN108461723B (en) 2020-08-18

Family

ID=63238734

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810140725.9A Active CN108461723B (en) 2018-02-11 2018-02-11 Silicon-based composite material for lithium ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108461723B (en)

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109599551A (en) * 2018-12-28 2019-04-09 安普瑞斯（南京）有限公司 A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery
CN109659529A (en) * 2018-12-17 2019-04-19 潍坊汇成新材料科技有限公司 A kind of preparation process of silicon-carbon cathode material
CN109713286A (en) * 2018-12-29 2019-05-03 安普瑞斯（南京）有限公司 A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery
CN109755500A (en) * 2018-12-05 2019-05-14 华为技术有限公司 A kind of silicon oxygen composite negative pole material and preparation method thereof
CN109786733A (en) * 2019-03-25 2019-05-21 中国科学院宁波材料技术与工程研究所 A kind of lithium ion battery negative material, preparation method and lithium ion battery
CN109817926A (en) * 2019-01-25 2019-05-28 溧阳天目先导电池材料科技有限公司 A kind of prelithiation material and preparation method thereof and lithium battery
CN109920987A (en) * 2019-02-20 2019-06-21 宁德新能源科技有限公司 Negative electrode material and electrochemical appliance and electronic device comprising the negative electrode material
CN109942001A (en) * 2019-04-02 2019-06-28 骆驼集团武汉光谷研发中心有限公司 A kind of silicium cathode material and preparation method thereof of spherical shape bayonet fittings
CN110391406A (en) * 2019-07-01 2019-10-29 深圳市比克动力电池有限公司 A kind of lithium ion battery silicon oxygen negative electrode material and preparation method thereof, lithium ion battery
CN110649264A (en) * 2019-09-30 2020-01-03 中国科学院宁波材料技术与工程研究所 Silicon-based negative electrode material and preparation method thereof
CN111048764A (en) * 2019-12-23 2020-04-21 北京理工大学重庆创新中心 Silicon-carbon composite material and preparation method and application thereof
CN111082013A (en) * 2019-12-18 2020-04-28 惠州亿纬创能电池有限公司 Preparation method of carbon-coated nitrogen-magnesium doped porous silicon-based composite material and lithium ion battery
CN111129458A (en) * 2019-12-20 2020-05-08 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of nano lithium silicide powder composite material, product and application thereof
CN111149242A (en) * 2019-12-30 2020-05-12 上海杉杉科技有限公司 Silicon-based lithium storage material and preparation method thereof
CN111180693A (en) * 2019-12-31 2020-05-19 安普瑞斯（南京）有限公司 Negative active material, preparation method and application thereof
WO2020103914A1 (en) * 2018-11-24 2020-05-28 华为技术有限公司 Silicon oxygen composite negative electrode material and fabrication method therefor
CN111342031A (en) * 2020-03-28 2020-06-26 兰溪致德新能源材料有限公司 Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
CN111342030A (en) * 2020-03-28 2020-06-26 兰溪致德新能源材料有限公司 Multi-element composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
WO2020140685A1 (en) * 2019-01-02 2020-07-09 Ningde Amperex Technology Limited Anode active material and anode using same, electrochemical device and electronic device
CN111430677A (en) * 2019-09-30 2020-07-17 蜂巢能源科技有限公司 Negative electrode material and preparation method thereof, negative electrode and lithium ion battery
CN111653737A (en) * 2020-04-20 2020-09-11 万向一二三股份公司 Silicon oxide composite material with gradient pre-lithiation structure and preparation method and application thereof
CN111710848A (en) * 2020-06-30 2020-09-25 贝特瑞新材料集团股份有限公司 Silica composite negative electrode material, preparation method thereof and lithium ion battery
CN112271289A (en) * 2020-10-30 2021-01-26 陕西煤业化工技术研究院有限责任公司 High-first-efficiency pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof
CN112289999A (en) * 2020-10-30 2021-01-29 陕西煤业化工技术研究院有限责任公司 Pre-lithiated silicon oxide/carbon composite material and preparation method and application thereof
WO2021068796A1 (en) * 2019-10-09 2021-04-15 中国石油化工股份有限公司 Negative electrode material, preparation method therefor and application thereof, and lithium-ion battery
CN112670462A (en) * 2020-03-31 2021-04-16 宁波杉杉新材料科技有限公司 Pre-lithiated silicon monoxide-graphite composite negative electrode material and preparation method and application thereof
CN112701267A (en) * 2020-12-30 2021-04-23 湖州杉杉新能源科技有限公司 Pre-lithiated silica composite material, negative pole piece, lithium battery and preparation method of pre-lithiated silica composite material
CN112736225A (en) * 2020-12-10 2021-04-30 安普瑞斯（南京）有限公司 Silica lithium particle aggregate and preparation method thereof, negative electrode material, pole piece and battery
WO2021136245A1 (en) * 2019-12-31 2021-07-08 安普瑞斯（南京）有限公司 Negative electrode active material for battery and preparation method therefor
CN113363432A (en) * 2021-04-21 2021-09-07 万向一二三股份公司 Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery
CN113991095A (en) * 2021-12-28 2022-01-28 安普瑞斯（南京）有限公司 Negative active material, preparation method thereof, electrode and battery
WO2022041831A1 (en) * 2020-08-31 2022-03-03 贝特瑞新材料集团股份有限公司 Silicon oxide composite material, negative electrode material, negative electrode and lithium ion battery, and preparation method therefor
WO2022062320A1 (en) * 2020-09-27 2022-03-31 溧阳天目先导电池材料科技有限公司 Negative electrode material on which metal element is gradient-doped and application thereof
CN114275785A (en) * 2021-12-24 2022-04-05 安徽科达新材料有限公司 High-first-efficiency silicon monoxide negative electrode and preparation method thereof
CN114303260A (en) * 2019-09-30 2022-04-08 株式会社Lg新能源 Composite anode active material, method for producing same, and anode comprising same
CN114388738A (en) * 2021-12-29 2022-04-22 湖北亿纬动力有限公司 Silicon-based negative electrode material and preparation method and application thereof
CN114464790A (en) * 2022-01-25 2022-05-10 四川金汇能新材料股份有限公司 Pre-lithiated silica composite material, preparation method and application
CN114464797A (en) * 2021-12-31 2022-05-10 长沙矿冶研究院有限责任公司 High-first-efficiency silica anode material and preparation method thereof
CN114759180A (en) * 2022-04-28 2022-07-15 中南大学 SiOx/lithium silicate composite material and preparation method and application thereof
EP3968409A4 (en) * 2019-07-26 2022-08-10 LG Energy Solution, Ltd. Composite anode active material, manufacturing method of same, anode comprising same, and secondary battery
WO2022205619A1 (en) * 2021-04-01 2022-10-06 广东凯金新能源科技股份有限公司 Silicon-carbon composite material having highly dense structure, and preparation method therefor and application thereof
WO2023102917A1 (en) * 2021-12-10 2023-06-15 宁德时代新能源科技股份有限公司 Negative electrode active material and preparation method therefor, secondary battery, battery module, battery pack, and power device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103400971A (en) * 2013-07-29 2013-11-20 宁德新能源科技有限公司 Silicon-based composite material and preparation method and applications thereof
CN106654194A (en) * 2016-11-07 2017-05-10 中国科学院化学研究所 Element-doped SiOx negative electrode composite material as well as preparation method and application thereof
CN106816594A (en) * 2017-03-06 2017-06-09 深圳市贝特瑞新能源材料股份有限公司 A kind of compound, its preparation method and the purposes in lithium rechargeable battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103400971A (en) * 2013-07-29 2013-11-20 宁德新能源科技有限公司 Silicon-based composite material and preparation method and applications thereof
CN106654194A (en) * 2016-11-07 2017-05-10 中国科学院化学研究所 Element-doped SiOx negative electrode composite material as well as preparation method and application thereof
CN106816594A (en) * 2017-03-06 2017-06-09 深圳市贝特瑞新能源材料股份有限公司 A kind of compound, its preparation method and the purposes in lithium rechargeable battery

Cited By (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020103914A1 (en) * 2018-11-24 2020-05-28 华为技术有限公司 Silicon oxygen composite negative electrode material and fabrication method therefor
EP3879605A4 (en) * 2018-11-24 2022-01-05 Huawei Technologies Co., Ltd. Silicon oxygen composite negative electrode material and fabrication method therefor
CN109755500A (en) * 2018-12-05 2019-05-14 华为技术有限公司 A kind of silicon oxygen composite negative pole material and preparation method thereof
CN109755500B (en) * 2018-12-05 2022-06-24 华为技术有限公司 Silica composite negative electrode material and preparation method thereof
CN115064671A (en) * 2018-12-05 2022-09-16 华为技术有限公司 Silica composite negative electrode material and preparation method thereof
CN115064671B (en) * 2018-12-05 2024-04-09 华为技术有限公司 Silicon-oxygen composite negative electrode material and manufacturing method thereof
CN109659529A (en) * 2018-12-17 2019-04-19 潍坊汇成新材料科技有限公司 A kind of preparation process of silicon-carbon cathode material
CN109599551A (en) * 2018-12-28 2019-04-09 安普瑞斯（南京）有限公司 A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery
CN109713286A (en) * 2018-12-29 2019-05-03 安普瑞斯（南京）有限公司 A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery
WO2020140685A1 (en) * 2019-01-02 2020-07-09 Ningde Amperex Technology Limited Anode active material and anode using same, electrochemical device and electronic device
CN111403693B (en) * 2019-01-02 2021-08-13 宁德新能源科技有限公司 Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same
US11145852B2 (en) 2019-01-02 2021-10-12 Ningde Amperex Technology Limited Anode active material and anode using same, electrochemical device and electronic device
JP2022504057A (en) * 2019-01-02 2022-01-13 寧徳新能源科技有限公司 Negative electrode active material materials and negative electrode sheets using them, electrochemical devices and electronic devices
CN111403693A (en) * 2019-01-02 2020-07-10 宁德新能源科技有限公司 Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same
JP7367008B2 (en) 2019-01-02 2023-10-23 寧徳新能源科技有限公司 Negative active material, negative electrode sheet using the same, electrochemical device, and electronic equipment
CN109817926A (en) * 2019-01-25 2019-05-28 溧阳天目先导电池材料科技有限公司 A kind of prelithiation material and preparation method thereof and lithium battery
CN109920987A (en) * 2019-02-20 2019-06-21 宁德新能源科技有限公司 Negative electrode material and electrochemical appliance and electronic device comprising the negative electrode material
WO2020168780A1 (en) * 2019-02-20 2020-08-27 Ningde Amperex Technology Limited Anode material, and electrochemical device and electronic device comprising the same
CN109786733A (en) * 2019-03-25 2019-05-21 中国科学院宁波材料技术与工程研究所 A kind of lithium ion battery negative material, preparation method and lithium ion battery
CN109942001B (en) * 2019-04-02 2022-08-09 骆驼集团武汉光谷研发中心有限公司 Silicon negative electrode material with spherical thorn-shaped structure and preparation method thereof
CN109942001A (en) * 2019-04-02 2019-06-28 骆驼集团武汉光谷研发中心有限公司 A kind of silicium cathode material and preparation method thereof of spherical shape bayonet fittings
CN110391406A (en) * 2019-07-01 2019-10-29 深圳市比克动力电池有限公司 A kind of lithium ion battery silicon oxygen negative electrode material and preparation method thereof, lithium ion battery
JP7438598B2 (en) 2019-07-26 2024-02-27 エルジー エナジー ソリューション リミテッド Composite negative electrode active material, method for producing the same, negative electrode containing the same, and secondary battery
EP3968409A4 (en) * 2019-07-26 2022-08-10 LG Energy Solution, Ltd. Composite anode active material, manufacturing method of same, anode comprising same, and secondary battery
US11891523B2 (en) 2019-09-30 2024-02-06 Lg Energy Solution, Ltd. Composite negative electrode active material, method of manufacturing the same, and negative electrode including the same
CN111430677A (en) * 2019-09-30 2020-07-17 蜂巢能源科技有限公司 Negative electrode material and preparation method thereof, negative electrode and lithium ion battery
CN110649264A (en) * 2019-09-30 2020-01-03 中国科学院宁波材料技术与工程研究所 Silicon-based negative electrode material and preparation method thereof
CN114303260A (en) * 2019-09-30 2022-04-08 株式会社Lg新能源 Composite anode active material, method for producing same, and anode comprising same
CN111430677B (en) * 2019-09-30 2022-05-24 蜂巢能源科技有限公司 Negative electrode material and preparation method thereof, negative electrode and lithium ion battery
WO2021068796A1 (en) * 2019-10-09 2021-04-15 中国石油化工股份有限公司 Negative electrode material, preparation method therefor and application thereof, and lithium-ion battery
CN111082013B (en) * 2019-12-18 2021-05-25 惠州亿纬创能电池有限公司 Preparation method of carbon-coated nitrogen-magnesium doped porous silicon-based composite material and lithium ion battery
CN111082013A (en) * 2019-12-18 2020-04-28 惠州亿纬创能电池有限公司 Preparation method of carbon-coated nitrogen-magnesium doped porous silicon-based composite material and lithium ion battery
CN111129458A (en) * 2019-12-20 2020-05-08 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of nano lithium silicide powder composite material, product and application thereof
CN111048764A (en) * 2019-12-23 2020-04-21 北京理工大学重庆创新中心 Silicon-carbon composite material and preparation method and application thereof
CN111149242B (en) * 2019-12-30 2024-01-23 上海杉杉科技有限公司 Silicon-based lithium storage material and preparation method thereof
CN111149242A (en) * 2019-12-30 2020-05-12 上海杉杉科技有限公司 Silicon-based lithium storage material and preparation method thereof
WO2021136245A1 (en) * 2019-12-31 2021-07-08 安普瑞斯（南京）有限公司 Negative electrode active material for battery and preparation method therefor
CN111180693B (en) * 2019-12-31 2021-06-04 安普瑞斯（南京）有限公司 Negative active material, preparation method and application thereof
CN111180693A (en) * 2019-12-31 2020-05-19 安普瑞斯（南京）有限公司 Negative active material, preparation method and application thereof
CN111342031A (en) * 2020-03-28 2020-06-26 兰溪致德新能源材料有限公司 Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
CN111342031B (en) * 2020-03-28 2022-11-29 兰溪致德新能源材料有限公司 Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
CN111342030A (en) * 2020-03-28 2020-06-26 兰溪致德新能源材料有限公司 Multi-element composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
CN112670462A (en) * 2020-03-31 2021-04-16 宁波杉杉新材料科技有限公司 Pre-lithiated silicon monoxide-graphite composite negative electrode material and preparation method and application thereof
CN111653737B (en) * 2020-04-20 2021-09-07 万向一二三股份公司 Silicon oxide composite material with gradient pre-lithiation structure and preparation method and application thereof
CN111653737A (en) * 2020-04-20 2020-09-11 万向一二三股份公司 Silicon oxide composite material with gradient pre-lithiation structure and preparation method and application thereof
CN111710848A (en) * 2020-06-30 2020-09-25 贝特瑞新材料集团股份有限公司 Silica composite negative electrode material, preparation method thereof and lithium ion battery
WO2022002057A1 (en) * 2020-06-30 2022-01-06 贝特瑞新材料集团股份有限公司 Silicon-oxygen composite negative electrode material, negative electrode, lithium-ion battery, and preparation methods therefor
WO2022041831A1 (en) * 2020-08-31 2022-03-03 贝特瑞新材料集团股份有限公司 Silicon oxide composite material, negative electrode material, negative electrode and lithium ion battery, and preparation method therefor
WO2022062320A1 (en) * 2020-09-27 2022-03-31 溧阳天目先导电池材料科技有限公司 Negative electrode material on which metal element is gradient-doped and application thereof
CN112271289A (en) * 2020-10-30 2021-01-26 陕西煤业化工技术研究院有限责任公司 High-first-efficiency pre-lithiated silicon monoxide negative electrode material and preparation method and application thereof
CN112289999A (en) * 2020-10-30 2021-01-29 陕西煤业化工技术研究院有限责任公司 Pre-lithiated silicon oxide/carbon composite material and preparation method and application thereof
CN112736225A (en) * 2020-12-10 2021-04-30 安普瑞斯（南京）有限公司 Silica lithium particle aggregate and preparation method thereof, negative electrode material, pole piece and battery
CN112701267A (en) * 2020-12-30 2021-04-23 湖州杉杉新能源科技有限公司 Pre-lithiated silica composite material, negative pole piece, lithium battery and preparation method of pre-lithiated silica composite material
WO2022205619A1 (en) * 2021-04-01 2022-10-06 广东凯金新能源科技股份有限公司 Silicon-carbon composite material having highly dense structure, and preparation method therefor and application thereof
CN113363432A (en) * 2021-04-21 2021-09-07 万向一二三股份公司 Negative plate containing silicon-based negative electrode material with high initial coulombic efficiency and lithium ion battery
WO2023102917A1 (en) * 2021-12-10 2023-06-15 宁德时代新能源科技股份有限公司 Negative electrode active material and preparation method therefor, secondary battery, battery module, battery pack, and power device
CN114275785A (en) * 2021-12-24 2022-04-05 安徽科达新材料有限公司 High-first-efficiency silicon monoxide negative electrode and preparation method thereof
CN113991095A (en) * 2021-12-28 2022-01-28 安普瑞斯（南京）有限公司 Negative active material, preparation method thereof, electrode and battery
WO2023124603A1 (en) * 2021-12-28 2023-07-06 博赛利斯（南京）有限公司 Negative electrode active material and preparation method therefor, electrode, and battery
CN113991095B (en) * 2021-12-28 2022-04-01 安普瑞斯（南京）有限公司 Negative active material, preparation method thereof, electrode and battery
CN114388738B (en) * 2021-12-29 2024-01-02 湖北亿纬动力有限公司 Silicon-based anode material and preparation method and application thereof
CN114388738A (en) * 2021-12-29 2022-04-22 湖北亿纬动力有限公司 Silicon-based negative electrode material and preparation method and application thereof
CN114464797A (en) * 2021-12-31 2022-05-10 长沙矿冶研究院有限责任公司 High-first-efficiency silica anode material and preparation method thereof
CN114464790B (en) * 2022-01-25 2023-06-02 四川金汇能新材料股份有限公司 Pre-lithiated silica composite material, preparation method and application
CN114464790A (en) * 2022-01-25 2022-05-10 四川金汇能新材料股份有限公司 Pre-lithiated silica composite material, preparation method and application
CN114759180A (en) * 2022-04-28 2022-07-15 中南大学 SiOx/lithium silicate composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN108461723B (en) 2020-08-18

Similar Documents

Publication Publication Date Title
CN108461723A (en) A kind of silicon based composite material and preparation method thereof for lithium ion battery
CN109599551B (en) Doped multilayer core-shell silicon-based composite material for lithium ion battery and preparation method thereof
CN111180691B (en) Double-layer carbon-coated silicon-based composite material and preparation method and application thereof
CN111554919B (en) Positive electrode active material, preparation method thereof and sodium ion battery
Zheng et al. Fabrication and understanding of Cu 3 Si-Si@ carbon@ graphene nanocomposites as high-performance anodes for lithium-ion batteries
Wang et al. Flexible SnSe2/N-doped porous carbon-fiber film as anode for high-energy-density and stable sodium-ion batteries
CN109713286A (en) A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery
CN111180692B (en) Negative electrode active material for battery and preparation method thereof
CN111146416B (en) Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery
CN108682787B (en) Lithium ion battery pole piece and preparation method thereof
Ding et al. Using potassium ferricyanide as a dopant to prepare K and Fe co-doped Li4Ti5O12
CN109411713A (en) The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery
CN100383037C (en) Carbon material and nano silicon composite materials and method for preparing same and use thereof
Liang et al. Synthesis and characterization of Fe-doped vanadium oxide nanorods and their electrochemical performance
CN112635727A (en) Silica particles with core-shell structure, preparation method thereof, negative electrode material and battery
Hai et al. Facile controlled synthesis of spinel LiMn2O4 porous microspheres as cathode material for lithium ion batteries
Li et al. Synthesis and electrochemical performance of Li4Ti5O12/Ag composite prepared by electroless plating
Chen et al. Y-doped Li4Ti5-xYxO12 with Y2Ti2O7 surface modification anode materials: Superior rate capability and ultra long cyclability for half/full lithium-ion batteries
Sun et al. In situ growth of core-shell structure of tremella fuciformis shaped SnS@ Sulfur doped carbon composite as anode materials for high performance lithium-ion batteries
CN112467097A (en) Negative electrode material, preparation method thereof, electrode and secondary battery
CN110931792B (en) Coated silicon-based material and preparation method thereof
Wu et al. Mixed-solvothermal synthesis and morphology-dependent electrochemical properties of α-Fe 2 O 3 nanoparticles for lithium-ion batteries
CN107195897B (en) Nano FeNbO4Graphene composite material and preparation and application thereof
CN111162269A (en) Negative electrode active material for battery and preparation method thereof
CN112467096B (en) Negative electrode material, preparation method thereof, electrode and secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: 210006 rooms 101, 102, 103, 104, 1 / F, building 3, No. 30, Fengzhan Road, Yuhuatai District, Nanjing City, Jiangsu Province

Patentee after: Bosellis (Nanjing) Co.,Ltd.

Address before: Room 101, 1 / F, building 3, No. 30, Fengzhan Road, Yuhuatai District, Nanjing City, Jiangsu Province, 210012

Patentee before: AMPRIUS (NANJING) Co.,Ltd.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230421

Address after: 210006 rooms 101, 102, 103, 104, 1 / F, building 3, No. 30, Fengzhan Road, Yuhuatai District, Nanjing City, Jiangsu Province

Patentee after: Bosellis (Nanjing) Co.,Ltd.

Patentee after: Boselis (Hefei) Co.,Ltd.

Address before: 210006 rooms 101, 102, 103, 104, 1 / F, building 3, No. 30, Fengzhan Road, Yuhuatai District, Nanjing City, Jiangsu Province

Patentee before: Bosellis (Nanjing) Co.,Ltd.