CN107887587A - Composite cathode material for lithium ion cell and preparation method thereof - Google Patents
Composite cathode material for lithium ion cell and preparation method thereof Download PDFInfo
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- CN107887587A CN107887587A CN201711094379.7A CN201711094379A CN107887587A CN 107887587 A CN107887587 A CN 107887587A CN 201711094379 A CN201711094379 A CN 201711094379A CN 107887587 A CN107887587 A CN 107887587A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 invention discloses a kind of composite cathode material for lithium ion cell and preparation method thereof, and nanometer silicon face progress oxidation processes are obtained into Surface coating the nano-silicon of silica；The nano-silicon that Surface coating has silica is well mixed with lithium source, obtains presoma；Gained presoma is placed in the nano silicon material for being heated in inert gas and obtaining being coated with lithium metasilicate, is washed, centrifuged, obtaining composite cathode material for lithium ion cell after drying.The present invention is matrix by using the uniform native oxide in nano silicon material surface, carry out the uniform cladding that in-situ chemical reaction realizes lithium metasilicate, the stability between nano-silicon and air or electrolyte interface is effectively improved, so as to greatly improve the chemical property of nano silicon material.
Description
Technical field
The present invention relates to lithium ion battery material preparing technical field, it particularly relates to which a kind of lithium ion battery is compound
Negative material and preparation method thereof.
Background technology
With the development of human society, energy crisis and environmental problem have become focus of concern, traditional energy
Clean and effective utilize and new energy source technology is developed into current main trend lithium ion battery because it has high property
Can security and advantages of environment protection, be at present the most promising and high energy green secondary cell of application prospect but
It is that every field rapidly improves especially country on accelerating new-energy automobile to the demand of battery energy density in recent years
Popularization and application, the energy density that novel high-energy densitybattery turns into the focus battery researched and developed at present depend primarily on electrode material
Material, new electrode materials support the development of electrochmical power source of new generation in the research of new non-carbon negative material, silica-base material because
Its low (0.02-0.6V vs.Li of high (3579mAh/g) removal lithium embedded current potential of theoretical specific capacity at room temperature+/ Li) environment-friendly storage
Measure the advantages that abundant and be considered as the lithium ion battery with high energy density negative material of future generation of most potential replacement graphite.
Silica-base material is primarily present two key issues first in large-scale application, and silicon belongs to alloy-type lithium storage materials,
During removal lithium embedded, the crystal structure of silicon, which changes, causes electrode material to produce huge bulk effect, causes electrode material
Powder of detached, active material lose effective electrical contact, show poor cyclical stability secondly, silicon materials are straight with electrolyte
Contact causes interface SEI films continued propagation constantly to consume electrolyte limited in battery system in the process and come from
The lithium of positive pole, ultimately resulting in battery capacity, decay is directed to these problems rapidly, and the method mainly solved is that material nano structure is set
Meter and novel electrolyte exploitation nano material due between the big short particle of lithium ion diffusion path of specific surface area headspace it is big
The advantages that, it can be obviously improved silica-base material chemical property but nano silicon material is due to specific surface area large surface activity
Height, silica is easily oxidized to, the nano silicon material after oxidation shows relatively low reversible specific capacity, or even loses electrification
The problem of oxidation for learning active nano silicon proposes more harsh requirement to its storage in actual production with application.
The native oxide of research nano surface silicon face can promote electrode/electrolyte interface to form stable SEI films,
Reasonable control surface oxidated layer thickness can improve the chemical property of material.Surface silica dioxide can occur as follows in the battery
Reaction: SiO2+ Li→Si+LixSiOy.Lithium silicate with preferable plasticity and mechanical performance can be stable in the presence of electrode/electro
Liquid interface is solved, it is a kind of fast-ionic conductor that can effectively protect internal silicon materials to corrode lithium metasilicate from electrolyte, is had than two
Still, in battery system, it is irreversible that silica is gradually transformed into lithium metasilicate reaction to the higher electronic conductivity of silica
Reaction, can equally consume the part lithium ion in battery.How effectively to realize and in-situ chemical reaction life occurs in nanometer silicon face
Into one layer of lithium metasilicate clad, and nano-silicon and electrolyte interface stability are greatly improved, there is good application prospect.
Lithium metasilicate is coated in lithium ion battery plus-negative plate and had been reported that：Chinese Patent Application No. 201610045279.4 carries
Go out and use lithium metasilicate graphite-doping lithium titanate anode material, its method is that direct addition lithium metasilicate carries out Surface coating, can not be to surface
Oxide layer is handled, and improves deficiency to the chemical property of material；Chinese Patent Application No. 201610887984.9 proposes one
Silicon/oxide composite negative pole material preparation method of the kind with lithium metasilicate boundary layer, its method are to utilize lithium hydroxide precipitation gold
Belong to oxide and association lithium silicate, can not effectively solve silicon surface oxidation sex chromosome mosaicism, the lithium source of the patent can only promote to generate
The lithium hydroxide of metal oxide, there is certain limitation.
The problem of in correlation technique, effective solution is not yet proposed at present.
The content of the invention
For the above-mentioned technical problem in correlation technique, the present invention proposes a kind of composite cathode material for lithium ion cell, energy
The native oxide on nano silicon material surface is enough utilized, in-situ chemical reaction life is carried out in nanometer silicon face by adding lithium source in advance
Into one layer of lithium metasilicate clad, realization greatly improves nano-silicon and electrolyte interface stability, while the volume that can alleviate silicon becomes
The destruction of electrode is turned to, preparation technology is simple, controllable, solves that nano-silicon is oxidizable and capacity plays abnormal problem.
To realize above-mentioned technical purpose, the technical proposal of the invention is realized in this way：
On the one hand, the present invention provides a kind of preparation method of composite cathode material for lithium ion cell, comprises the following steps：
Step 1）：Nanometer silicon face progress oxidation processes are obtained into Surface coating the nano-silicon of silica；
Step 2）：The nano-silicon that Surface coating has silica is well mixed with lithium source, obtains presoma；
Step 3）：By step 2）Gained presoma is placed in the nano silicon material that heating in inert gas obtains being coated with lithium metasilicate；
Step 4）：Gained nano silicon material is washed, centrifuged, obtains lithium ion battery composite cathode material after drying
Material.
Further, the Surface coating has silica in the nano-silicon of silica to account for its total mass ratio as 1 ~ 20%.
Preferably, the mass ratio is 1%, 2%, 5%, 8%, 10%, 15%, 20%.
Further, the step 1）Middle nano-silicon is silicon nanosphere, silicon nanowires, porous nano silicon, silicon substrate composite wood
One or more in material.Preferably, silicon based composite material is silicon/graphite, silicon/graphene etc..
Further, the step 1）The mode of middle oxidation processes includes：Nano-silicon exposes autoxidation in atmosphere, adopts
Nanometer silicon face is aoxidized with oxidant and one in by the way of Low Temperature Heat Treatment aoxidizes to nanometer silicon face
Kind is several.The nano-silicon exposes autoxidation in atmosphere, passes through the oxidizing process of simulation material in actual applications.Institute
It can be that nano silica fume is slowly added in hydrogenperoxide steam generator to state and oxidation is carried out to nanometer silicon face using oxidant, peroxide
Change hydrogen concentration and be not higher than 30%, after ultrasonic disperse in 60 ~ 90 DEG C of oil baths magnetic agitation 0.5 ~ 6 hour, silica flour in filtering solution,
Cleaned with deionized water and ethanol, be finally dried in vacuo successively, that is, complete the surface treatment process of nano-silicon.The use
It can be that nano silicon material is placed in into heating and thermal insulation certain time in tube furnace that Low Temperature Heat Treatment, which carries out oxidation to nanometer silicon face,
Heating-up temperature is not higher than 600 DEG C.
Further, it is described nanometer silicon face to be aoxidized using oxidant, the oxidant include hydrogen peroxide,
Hydrogen peroxide and concentrated sulfuric acid mixed solution, concentrated sulfuric acid solution etc..
Further, the lithium source is lithium carbonate, lithium oxalate, lithium acetate, lithium phosphate, lithium tartrate, lithium citrate, molybdic acid
One or more in lithium, lithium titanate.
Further, lithium has the mol ratio of silica in the nano-silicon of silica to be with Surface coating in the lithium source
0.4~8.Preferably, the mol ratio is 0.4,0.8,1.0,1.5,2.0,2.5,3.0,4.0,5.0,6.0,7.0,8.0.
Further, the step 2）Described in Surface coating have silica nano-silicon dissolving in a solvent after and lithium
Source ultrasonic disperse is uniform, obtains being coated with the nano silicon material of lithium metasilicate after removal solvent.
Further, solvent lithium source selected by is reasonably selected, preferably water, ethanol etc.；It is preferred that water
For deionized water.
Further, it is described remove solvent mode include solvent evaporation, forced air drying, vacuum drying, freeze-drying,
One or more in spray drying.
Further, the step 2）Described in Surface coating have the nano-silicon of silica and lithium source solid phase mixing uniform
Obtain being coated with the nano silicon material of lithium metasilicate.
Further, the solid phase mixing includes the one or more in grinding, high-energy ball milling, high energy sand milling.
Further, step 3）Described in inert gas include argon gas, hydrogen-argon-mixed body, nitrogen etc..
Further, step 3）Described in the temperature control that heats at 550 ~ 950 DEG C, the temperature control is 550 ~ 950
DEG C keep 1 ~ 12h.Preferably, the temperature control is at 900 DEG C, 700 DEG C, 550 DEG C；The temperature hold-time be 1h, 2h,
5h、10h、12h。
Further, the step 3）Middle lithium metasilicate includes a lithium metasilicate, lithium bisilicate, one kind in five lithium metasilicates or several
Kind.
Further, the step 3）The obtained nano silicon material surface for being coated with lithium metasilicate is also wrapped on carbon-coating.
Further, the step 4）The middle solvent used that washs is ethanol or deionized water.
Further, the step 4）It is middle dry using vacuum drying.
On the other hand, the present invention provides composite cathode material for lithium ion cell prepared by a kind of method of the present invention,
Including nano-silicon and the lithium silicate for being coated on nanometer silicon face.
On the other hand, the present invention provides composite cathode material for lithium ion cell prepared by a kind of method of the present invention,
Including nano-silicon, it is coated on the lithium silicate and carbon-coating of nanometer silicon face.
On the other hand, the present invention provides a kind of negative electrode of lithium ion battery, including is answered with lithium ion battery of the present invention
Negative material is closed to prepare for raw material.
On the other hand, the present invention provides a kind of lithium ion battery, including negative electrode of lithium ion battery of the present invention.
The present invention is the interface stability of raising nano-silicon and electrolyte, solves the problems, such as that nanometer silicon face is oxidizable, if
A kind of silicon dioxide layer primary based on nanometer silicon face is counted, using in-situ chemical reaction generation receiving with lithium metasilicate clad
Rice silicium cathode material, i.e. composite cathode material for lithium ion cell.The design concept total as one, nano silicon material is as activity
Material, surface generates one layer of nano silicon dioxide layer by autoxidation or oxidation processes, by the nano silicon material and lithium after oxidation
Source mixes, by high-temperature process so that silica and lithium source reaction generation lithium silicate, are answered so as to which lithium ion battery be prepared
Close negative material.
In the preparation process of the present invention, if the lithium source of selection has macromolecule functional group, high temperature in an inert atmosphere
The carbon-coating generation of part is also had while reaction, so as to form double protective layer structures of lithium metasilicate in situ and pyrolytic carbon.
The aerial storge quality of composite cathode material for lithium ion cell prepared by the present invention greatly improves, in the battery
Electrode/electrolyte interface stability and electrochemical cycle stability be improved significantly.
The present invention is using nano silicon material is oxidizable present in actual application, capacity plays abnormal etc. ask
Topic, based on nanometer silicon face native oxide, surface lithium metasilicate cladding is carried out using in-situ chemical reaction.Synthesized lithium metasilicate
With good mechanical performance and ionic conductivity, in-situ chemical coats the uniform cladding that can realize silicon face, can be preferably
Completely cut off erosion of the electrolyte to silicon.The lithium silicate generated can be stable in the presence of electrode/electrolyte interface, will not consume electricity
The lithium of electrolyte or positive pole in pond body system.Lithium metasilicate be not involved in deintercalation reaction, be not in phase transformation and make clad come off or
Phenomena such as person's efflorescence.In addition, lithium silicate shows more preferable stability in atmosphere, so as to preferably improve nano silicon material
Storge quality in actual applications.
Beneficial effects of the present invention：Composite cathode material for lithium ion cell prepared by the present invention is by using nano silicon material
The uniform native oxide in surface is matrix, carries out the uniform cladding that in-situ chemical reaction realizes lithium metasilicate, effectively improves nanometer
Stability between silicon and air or electrolyte interface, so as to greatly improve the chemical property of nano silicon material.
The preparation method of composite cathode material for lithium ion cell provided by the invention is by using lithium source and the height of nano-silicon
Temperature reaction, preparation flow is short, cost is low, and controllability is high, and resulting materials stability is high, is adapted to produce application in enormous quantities.
Have no any at present and composite cathode material for lithium ion cell is prepared using in-situ chemical reaction on being aoxidized based on silicon
Report.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to institute in embodiment
The accompanying drawing needed to use is briefly described, it should be apparent that, drawings in the following description are only some implementations of the present invention
Example, for those of ordinary skill in the art, on the premise of not paying creative work, can also be obtained according to these accompanying drawings
Obtain other accompanying drawings.
Fig. 1 is the XRD spectrum of the resulting materials of the preferred embodiment of the invention 1；
Fig. 2 is the TEM collection of illustrative plates of the resulting materials of the preferred embodiment of the invention 1；
Fig. 3 is the cycle performance figure that the resulting materials of the preferred embodiment of the invention 1 are assembled into button cell；
Fig. 4 is the Microstructure characterization collection of illustrative plates of the resulting materials of the preferred embodiment of the invention 2；
Fig. 5 is the cycle performance figure that the resulting materials of the preferred embodiment of the invention 2 are assembled into button cell；
Fig. 6 is the XRD spectrum of the resulting materials of the preferred embodiment of the invention 3；
Fig. 7 is the XPS collection of illustrative plates of the resulting materials of the preferred embodiment of the invention 3.
In figure：Silicon silicon, intensity intensity, theta θ, degree °, voltage voltages,
Specific capacity specific capacities, cycle number periods, charge chargings, discharge electric discharges,
Counts is counted, binding energy combination energy.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained, belong to what the present invention protected
Scope.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
Identical technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain
Except there is a special instruction, the various reagents raw material used in the present invention be can be commercially commodity or can
To pass through product made from known method
Embodiment 1
After taking 0.8g silicon nanoparticles to be put in humid air one week, nano-silicon is dissolved at 10 DEG C in 50mL deionized waters.With
Afterwards add 0.05g lithium carbonates, after stirring, ultrasonic disperse, during control temperature it is constant, then solution is freeze-dried,
Obtain presoma.
Gained presoma is placed in argon gas atmosphere tube furnace, 900 DEG C are heated to 5 DEG C/min, constant temperature 2h is naturally cold
But obtain being coated with the nano silicon material of lithium metasilicate.
The nano silicon material for being coated with lithium metasilicate then is washed with deionized, high speed centrifugation, is dried in vacuo to obtain
Composite cathode material for lithium ion cell.
The physical and chemical performance of gained composite cathode material for lithium ion cell, which characterizes, sees Fig. 1, Fig. 2, Fig. 3.Show from Fig. 1 XRD results
Show composite cathode material for lithium ion cell surface by lithium metasilicate and lithium metasilicate phase composition, without other dephasign peaks, and the feature of silicon
Peak still keeps preferable crystal formation.Scheme from Fig. 2 TEM it can be seen that nanometer silicon face has the uniform titanium dioxide of a layer thickness after aoxidizing
Silicon, after treatment, surface amorphous silica layer are transformed into one layer of uniform lithium silicate.Gained lithium ion battery is answered
Conjunction negative material is assembled into button cell and surveys its cycle performance, as shown in figure 3, under 200 mA/g current densities, is received after oxidation
Rice silicon capacity, which plays, only has 2400 mAh/g, and far below its theoretical specific capacity, and coulombic efficiency only has 76% first, and passes through former
Coulombic efficiency brings up to 86% to nano silicon material after the chemical reaction handling of position first.It is in addition, bent by discharge and recharge before and after the processing
Line does not change, and shows that lithium metasilicate does not have electro-chemical activity, and composite cathode material for lithium ion cell specific capacity reduces after cladding,
This is due to that reversible specific capacity is based on all silicon materials, and the introducing of lithium metasilicate reduces the mass ratio of active silicon materials.From circulation
Gained composite cathode material for lithium ion cell cycle performance cyclical stability is largely increased after performance can be seen that processing,
This is attributed to the stability that lithium metasilicate clad improves silicon and electrolyte interface.
Embodiment 2
0.5g nano-silicons are taken to add the hydrogen peroxide that 50ml concentration is 10%, after stirring ultrasonic disperse, vacuum is done at 80 DEG C after filtering
It is dry.At room temperature, nano-silicon after processing is dissolved in 50ml ethanol, after stirring ultrasonic disperse, adds 0.5g anhydrous acetic acid lithiums, after
The uniform 1h of continuous stirring ultrasonic disperse.Then solution is freeze-dried, obtains presoma.
Gained presoma is placed in argon gas atmosphere tube furnace, 700 DEG C are heated to 5 DEG C/min, constant temperature 5h is naturally cold
But obtain being coated with the nano silicon material of lithium metasilicate and carbon-coating.
The nano silicon material for being coated with lithium metasilicate and carbon-coating, after being centrifuged at a high speed, vacuum then is washed with deionized
It is dried to obtain composite cathode material for lithium ion cell.
Gained composite cathode material for lithium ion cell Microstructure characterization is shown in Fig. 4, and cycle performance is shown in Fig. 5.Anhydrous acetic acid lithium
（C2H3LiO2）The main water of high temperature thermal decomposition product, lithia and organic carbon phase under an inert atmosphere, lithia are given birth to silica
Into lithium silicate, organic carbon phase is coated on material surface and forms amorphous carbon layer.From fig. 4, it can be seen that after treatment, nanometer
Silicon still remains intact crystal formation and spherical structure, and surface is the clad that one layer of lithium metasilicate and amorphous carbon coexist.By gained lithium
Ion battery composite negative pole material is assembled into button cell and surveys its cycle performance, as shown in figure 5, under the conditions of high-current test,
After oxidation nanometer silicon cycling after 200 weeks capability retention only have 24.%, and gained lithium ion battery composite cathode after treatment
Material capacity remains 70.9%.From cycle performance as can be seen that composite cathode material for lithium ion cell cyclicity obtained by after processing
Energy cyclical stability is largely increased, and this is attributed to the clad that designed lithium metasilicate coexists with carbon.Lithium metasilicate and carbon-coating
Electrolyte is effectively hindered to be contacted with the direct of silicon, electrolyte can form stable solid electrolyte layer, tool on carbon-coating surface
There are the lithium silicate of good mechanical properties and carbon-coating effectively to suppress the volumetric expansion of silicon.
Embodiment 3
Take nano-silicon to add the hydrogen peroxide that 50ml concentration is 10%, after stirring ultrasonic disperse, be dried in vacuo after filtering at 80 DEG C.
At room temperature, it is 2 according to mass ratio by nano-silicon after processing and lithium oxalate：1 mixing.Mixture is placed in high speed vibration ball mill
With 1200 turns/min ball milling 3h, presoma is obtained.
Gained presoma is placed in argon gas atmosphere tube furnace, 900 DEG C are heated to 5 DEG C/min, constant temperature 5h is naturally cold
But obtain being coated with the nano silicon material of lithium metasilicate.
The nano silicon material for being coated with lithium metasilicate then is washed with deionized, is dried in vacuo and obtains after being centrifuged at a high speed
Composite cathode material for lithium ion cell.
Fig. 6 is the XRD spectrum of gained composite cathode material for lithium ion cell, the results showed that lithium ion battery composite cathode material
Material is made up of nano-silicon, lithium bisilicate and five lithium metasilicates, and nano-silicon still remains intact crystal structure, and without other dephasign materials
Generation.Fig. 7 is the XPS collection of illustrative plates of nano-silicon and lithium metasilicate cladding nano-silicon after oxidation, the results showed that, by oxidation processes, nanometer
Silicon face silica is far above silicon features peak.Element silicon characteristic peak after lithium metasilicate is handled in resulting materials silica
Reduce.The new characteristic peak occurred between 100-103, the element silicon in lithium metasilicate is corresponded to, this explanation nanometer silicon face is main
Composition is lithium metasilicate phase.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (10)
1. a kind of preparation method of composite cathode material for lithium ion cell, it is characterised in that comprise the following steps：
Step 1）：Nanometer silicon face progress oxidation processes are obtained into Surface coating the nano-silicon of silica；
Step 2）：The nano-silicon that Surface coating has silica is well mixed with lithium source, obtains presoma；
Step 3）：By step 2）Gained presoma is placed in the nano silicon material that heating in inert gas obtains being coated with lithium metasilicate；
Step 4）：Gained nano silicon material is washed, centrifuged, obtains lithium ion battery composite cathode material after drying
Material.
2. preparation method according to claim 1, it is characterised in that the Surface coating has in the nano-silicon of silica
Silica accounts for its total mass ratio as 1 ~ 20%；
The step 1）Middle nano-silicon is silicon nanosphere, silicon nanowires, porous nano silicon, one kind in silicon based composite material or several
Kind.
3. preparation method according to claim 1, it is characterised in that the step 1）The mode of middle oxidation processes includes：
Nano-silicon exposes autoxidation in atmosphere, nanometer silicon face is aoxidized using oxidant and using Low Temperature Heat Treatment to receiving
One or more in the mode that rice silicon face is aoxidized.
4. preparation method according to claim 1, it is characterised in that the lithium source be lithium carbonate, lithium oxalate, lithium acetate,
One or more in lithium phosphate, lithium tartrate, lithium citrate, lithium molybdate, lithium titanate；
It is 0.4 ~ 8 that lithium and Surface coating, which have the mol ratio of silica in the nano-silicon of silica, in the lithium source.
5. preparation method according to claim 1, it is characterised in that step 2）In, the Surface coating has silica
Nano-silicon dissolving in a solvent after it is uniform with lithium source ultrasonic disperse, obtain being coated with the nano-silicon material of lithium metasilicate after removal solvent
Material；Or the Surface coating has the nano-silicon of silica and lithium source solid phase mixing uniformly to obtain being coated with the nano-silicon of lithium metasilicate
Material；
The mode for removing solvent includes one in solvent evaporation, forced air drying, vacuum drying, freeze-drying, spray drying
Kind is several；
The solid phase mixing includes the one or more in grinding, high-energy ball milling, high energy sand milling.
6. preparation method according to claim 1, it is characterised in that step 3）Described in inert gas include argon gas, nitrogen
Gas；
Step 3）Described in the temperature control that heats at 550 ~ 950 DEG C, the temperature control keeps 1 ~ 12h at 550 ~ 950 DEG C；
The step 3）Middle lithium metasilicate includes the one or more in a lithium metasilicate, lithium bisilicate, five lithium metasilicates.
7. preparation method according to claim 1, it is characterised in that the step 3）What is obtained is coated with receiving for lithium metasilicate
Rice silicon materials surface is also wrapped on carbon-coating.
8. composite cathode material for lithium ion cell prepared by a kind of any described method of claim 1 ~ 7, it is characterised in that bag
Include nano-silicon and be coated on the lithium silicate of nanometer silicon face；
Or including nano-silicon, be coated on the lithium silicate and carbon-coating of nanometer silicon face.
9. a kind of negative electrode of lithium ion battery, it is characterised in that including with the lithium ion battery composite cathode material described in claim 8
Expect to prepare for raw material.
10. a kind of lithium ion battery, it is characterised in that including the negative electrode of lithium ion battery described in claim 9.
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| CN112186188A (en) * | 2020-09-29 | 2021-01-05 | 东莞东阳光科研发有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN112366301A (en) * | 2020-11-11 | 2021-02-12 | 宁夏博尔特科技有限公司 | Silicon/silicon oxide/carbon composite negative electrode material for lithium ion battery and preparation method thereof |
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| CN112670489A (en) * | 2019-12-16 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, electrode, lithium ion battery and preparation method and application thereof |
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| CN112713262A (en) * | 2019-12-16 | 2021-04-27 | 宁波杉杉新材料科技有限公司 | Silicon monoxide composite material, electrode, lithium ion battery and preparation method and application thereof |
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| CN112670489A (en) * | 2019-12-16 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Silicon-carbon composite material, electrode, lithium ion battery and preparation method and application thereof |
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| EP4078634B1 (en) * | 2019-12-20 | 2023-09-20 | Aalto University Foundation sr | An electrode for a supercapacitor comprising a grass like dielectric |
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| CN114373891A (en) * | 2021-12-31 | 2022-04-19 | 远景动力技术(江苏)有限公司 | Composite lithium negative electrode and application thereof |
| CN114759180A (en) * | 2022-04-28 | 2022-07-15 | 中南大学 | SiOx/lithium silicate composite material and preparation method and application thereof |
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