CN109103425A - Negative electrode material, cathode and the battery with the cathode - Google Patents
Negative electrode material, cathode and the battery with the cathode Download PDFInfo
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- CN109103425A CN109103425A CN201810113661.3A CN201810113661A CN109103425A CN 109103425 A CN109103425 A CN 109103425A CN 201810113661 A CN201810113661 A CN 201810113661A CN 109103425 A CN109103425 A CN 109103425A
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- 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
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- 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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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
A kind of negative electrode material includes at least Si oxide SiOxAnd carbon material, wherein 1≤x≤2.Cathode with the negative electrode material, the preparation method of battery and the negative electrode material with the cathode.Negative electrode material with porous structure, cushion space can be provided for the bulk effect of charge and discharge process Si oxide, the volume change when silicon oxide particles of nano-scale reduce ion insertion and deviate from simultaneously, the bulk effect for reducing silicon based anode material ensure that the cycle performance of negative electrode material.
Description
The application is entitled negative electrode material and preparation method thereof, cathode, tool filed in applicant on August 29th, 2013
There is the battery of the cathode, application No. is the divisional applications of the Chinese invention patent application of 201310383201.x.
Technical field
The present invention relates to a kind of negative electrode material more particularly to a kind of negative electrode materials containing Si oxide.
The invention further relates to a kind of cathode containing Si oxide negative electrode material.
The invention further relates to a kind of batteries containing Si oxide negative electrode material.
Background technique
Lithium ion battery compared with traditional secondary cell, have open-circuit voltage is high, energy density is big, long service life,
It is the advantages that memory-less effect, very widely used.Develop a kind of safety, low cost, high capacity, stable cycle performance is quickly filled
The lithium ion battery of electric discharge is the urgent need of the technological progress of portable electronic device and electric car.
Commercial lithium ion battery negative material is carbons negative electrode material at present, and negative electrode material made of carbon material has connect
The theoretical capacity 372mAh/g of nearly graphite, therefore, a large amount of research start to turn to the novel cathode found and can substitute carbon material
Material, wherein silicon is widely studied because it is with high theoretical capacity 4200mAh/g and low intercalation potential, still, due to
The electric conductivity of silicon is bad, and the battery containing silicium cathode material, there are serious bulk effect, causes to bear in charge and discharge process
Pole material occurs dusting, falls off and gradually lose electrical contact, finally makes the cycle performance of battery very poor.
In view of the above-mentioned problems, many researchs are all asked in electric conductivity, the bulk effect etc. for being dedicated to improveing silicon based anode material
Topic.
United States Patent (USP) US20080261116A1 discloses the method that silicon particle is deposited on carbon material surface, and utilization is siliceous
Precursor, which is contacted by gas phase and decomposed with carbon material, forms silicon particle coating in carbon material surface；US20080280207A1 is public
It has opened on the continuous film surface of the silicon particle composition of nano-scale, deposition of carbon nanotubes prepares the cathode material of lithium ion battery
Material；But these preparation methods process is complicated, and preparation cost is high, is not suitable for being mass produced.
CN101153358A mixes high molecular polymer, silicon powder and graphite powder, ball milling, and in inert gas high temperature carbon
Change processing prepares a kind of lithium ion battery negative material；CN100344016C mixes silicon powder and carbohydrate, utilizes dense sulphur
Acid processing, and form lithium ion battery silicon/carbon graphite negative electrode material；CN100370959A by silicon powder and graphite mixing and ball milling, then
Carbohydrate is added, using sulfuric acid treatment, washs, it is dry.It crushes and forms silicon/carbon graphite negative electrode material.These methods exist
When preparing silicon based anode material, some are needed using a large amount of organic solvent, dispersing agent or binder, some are needed at high temperature
The clad structure of product could be completed and need to destroy by break process, increases production cost and is brought simultaneously to industrialization
It is greatly inconvenient.
Summary of the invention
The present invention is intended to provide a kind of capacity height, stable cycle performance, the simple negative electrode material of preparation method.
To achieve the above object, the technical scheme is that a kind of negative electrode material, the negative electrode material include at least silicon
Oxide S iOxAnd carbon material, wherein 1≤x≤2.
Preferably, at least partly described Si oxide SiOxFor the nano particle with cavernous structure.
Preferably, the Si oxide SiOxThe specific gravity range for accounting for the negative electrode material is 5-70%, and the carbon material accounts for
The specific gravity range of the negative electrode material is 30-95%.
Preferably, the negative electrode material further includes metallic copper, and the specific gravity range that the metallic copper accounts for the negative electrode material is
0.5-30%.
Preferably, the metallic copper is coated on the Si oxide SiOx, the carbon material is coated on the Si oxide
SiOxAnd metallic copper.
The present invention also provides a kind of negative electrode material, the negative electrode material includes Si oxide SiOx, graphene and unordered
Carbon material, wherein 1≤x≤2.
Preferably, it is 0.5-20% that the graphene, which accounts for the specific gravity range of the negative electrode material,.
Preferably, the unordered carbon material is coated on the Si oxide SiOxAnd graphene.
The present invention also provides a kind of cathode, the cathode includes negative electrode material as described above.
The present invention also provides a kind of batteries, including anode, cathode and the electrolyte between anode and cathode, institute
Stating cathode includes negative electrode material as described above.
The present invention also provides a kind of preparation method of negative electrode material, the preparation method includes the following steps:
Carbon material precursor is dissolved in the first solvent, Si oxide is added into the first solvent dissolved with carbon material precursor
SiOx, the second solvent is added after mixing, the Si oxide SiO for coating carbon material precursorxPrecipitating, precipitated product drying is laggard
Row high-temperature process obtains the Si oxide SiO of carbon material claddingx。
The present invention also provides a kind of preparation method of negative electrode material, the preparation method includes the following steps:
Carbon material precursor is dissolved in the first solvent, Si oxide is added into the first solvent dissolved with carbon material precursor
SiOxAnd graphene, the second solvent is added after mixing, the Si oxide SiO for coating carbon material precursorxIt is precipitated with graphene, it will
High-temperature process is carried out after precipitated product is dry, obtains the Si oxide SiO of unordered carbon material claddingxAnd graphene.
The present invention also provides a kind of preparation method of negative electrode material, the preparation method includes the following steps:
By Si oxide SiOxIt is dispersed in copper nitrate solution, the solvent in dry removal solution, by the silicon oxygen after drying
Compound SiOx1-4h is handled at 170-300 DEG C of temperature with copper nitrate, obtains the Si oxide SiO of oxidation copper cladx；
Carbon material precursor is dissolved in the first solvent, oxidation copper-clad is added into the first solvent dissolved with carbon material precursor
The Si oxide SiO coveredx, the second solvent is added after mixing, the Si oxide SiO for the oxidation copper clad for coating carbon material precursorx
Precipitating will carry out high-temperature process after precipitated product drying, be pyrolyzed carbon material precursor, copper oxide is reduced into copper, obtains carbon material
The Si oxide SiO of the copper clad of claddingx。
Preferably, first solvent is selected from dimethylformamide, dimethyl sulfoxide, sulfolane or N- crassitude
One of ketone.
Preferably, second solvent includes one of water, methanol, ethyl alcohol or propyl alcohol.
Preferably, the product after high-temperature process is dissolved into part Si oxide SiO with hydrogen fluoride solutionx, had
Porous negative electrode material.
Preferably, the carbon material precursor is selected from polyacrylonitrile, polypyrrole, polyvinyl chloride, Kynoar, polyethylene
At least one of alcohol, polystyrene, phenolic resin, epoxy resin, coal tar asphalt, asphalt, sucrose or glucose.
Preferably, the temperature range when high-temperature process is 600-1200 DEG C, and high-temperature process time range is 1-6h.
Compared with prior art, negative electrode material has porous structure in the present invention, is Si oxide in charge and discharge process
Bulk effect provides space, while the silicon oxide particles of nano-scale reduce volume change when ion is embedded in and deviates from,
Further improve the bulk effect of negative electrode material；And metallic copper and graphene then improve the electric conductivity of negative electrode material, favorably
In the fast transfer of charge, so that negative electrode material capacity with higher, stable cycle performance.Cathode material provided by the invention
Preparation method is simple for material, has industrial prospect.
Detailed description of the invention
The invention will be further described with embodiment with reference to the accompanying drawing.
Fig. 1 is the negative electrode material SiO that embodiment 1 provides2The X-ray diffractogram of/C；
Fig. 2 is the negative electrode material SiO that embodiment 1 provides2The TG and DTA curve of/C；
Fig. 3 is the scanning electron microscope diagram for the negative electrode material SiO/C that embodiment 2 provides；
Fig. 4 is the negative electrode material SiO that embodiment 3 provides2The X-ray diffractogram of/Cu/C；
Fig. 5 is the negative electrode material SiO that embodiment 3 provides2The TG and DTA curve of/Cu/C；
Fig. 6 is the SiO for the negative electrode material C cladding that embodiment 4 provides and the SEM figure of graphene；
The relation curve of voltage and specific capacity when Fig. 7 is the battery constant current charging-discharging of the offer of embodiment 5；
Cycle performance figure when Fig. 8 is the battery constant current charging-discharging of the offer of embodiment 5；
Fig. 9 be embodiment 5 provide battery with different current density charge and discharge when cycle performance figure；
Figure 10 be embodiment 6 provide battery with current density 55mA/g charge and discharge when cycle performance figure；
Figure 11 is the battery of the offer of embodiment 6 with voltage when current density 55mA/g charge and discharge and specific capacity relational graph；
Figure 12 be embodiment 6 provide battery with current density 110mA/g charge and discharge when cycle performance figure；
Cycle performance figure when Figure 13 is the battery constant current charging-discharging of the offer of embodiment 7；
Figure 14 be embodiment 7 provide battery with different current density charge and discharge when cycle performance figure；
Voltage and specific capacity relational graph when Figure 15 is the battery constant current charging-discharging of the offer of embodiment 8；
Cycle performance figure when Figure 16 is the battery constant current charging-discharging of the offer of embodiment 8；
Voltage and specific capacity relational graph when Figure 17 is the battery constant current charging-discharging of the offer of embodiment 9；
Figure 18 be embodiment 9 provide battery with current density 55mA/g charge and discharge when cycle performance figure；
Figure 19 be embodiment 9 provide battery with current density 110mA/g charge and discharge when cycle performance figure；
Voltage and specific capacity relational graph when Figure 20 is the battery constant current charging-discharging of the offer of embodiment 11；
Cycle performance figure when Figure 21 is the battery constant current charging-discharging of the offer of embodiment 11；
Figure 22 be embodiment 11 provide battery with different current density charge and discharge when cycle performance figure；
Cycle performance figure when Figure 23 is the battery constant current charging-discharging of the offer of embodiment 13；
Figure 24 be embodiment 15 provide battery with current density 55mA/g charge and discharge when cycle performance figure；
Figure 25 be embodiment 15 provide battery with current density 110mA/g charge and discharge when cycle performance figure；
Figure 26 be embodiment 15 provide battery with different current density charge and discharge when cycle performance figure；
Figure 27 be embodiment 17 provide battery with different current density charge and discharge when cycle performance figure；
Cycle performance figure when Figure 28 is the battery constant current charging-discharging of the offer of comparative example 1；
Specific embodiment
A kind of negative electrode material applied in electrochemical appliance, the basic composition with silica-base material, electrochemical appliance packet
Battery is included but be not limited only to, using the battery of such material, such as portable electronic device, electric tool, electricity can be applied to
The fields such as electrical automobile.
A kind of negative electrode material includes at least Si oxide SiOxAnd carbon material, wherein 1≤x≤2.Negative electrode material has more
Pore structure, the aperture size of negative electrode material are nanoscale or submicron order.In negative electrode material, Si oxide SiOxAccount for negative electrode material
Specific gravity range be 5-70%, carbon material account for negative electrode material specific gravity range be 30-95%.
When negative electrode material is applied in battery, the porous structure of negative electrode material can be Si oxide in charge and discharge process
SiOxVolume change sufficient cushion space is provided, to guarantee the cycle performance of negative electrode material well.
Specifically, Si oxide SiOxIncluding SiO or SiO2, at least part of Si oxide SiOxFor with cavernous structure
Nano particle, the particle size range of nano particle is 1-100nm.
Carbon material is coated on Si oxide SiOx, specifically, carbon material is coated on the Si oxide SiO with cavernous structurex
On the surface and hole wall of nano particle.The form of carbon material includes carbon film, carbon nano-particles, carbon nanotube, carbon nanocoils or carbon
One of nanofiber is a variety of, and in the particular embodiment, carbon material is disordered carbon (disordered carbon).
Relative to elemental silicon, Si oxide SiOxTheoretical specific capacity it is slightly smaller, with Si oxide SiOxThe increasing of middle oxygen content
Add, specific capacity can reduce, but cycle performance but significantly improves.With the nanometer Si oxide of cavernous structure in the present invention
SiOx, the volume change absolute value very little in battery charge and discharge process, can slow down negative electrode material structure destroy.Although nanometer ruler
Very little Si oxide SiOxThe bulk effect occurred in improving battery charge and discharge process has obvious effects on, but nano-scale
Si oxide SiOxThere are agglomerations, are possible to lose electrical contact and fail between the silicon oxide particles after reunion.For
This problem, negative electrode material provided by the invention have clad structure, and Si oxide cladding has excellent electron electric conductivity
Carbon material.
Further, negative electrode material further includes metallic copper, and the specific gravity range that metallic copper accounts for negative electrode material is 0.5-30%.Gold
Belong to copper-clad and be overlying on Si oxide, carbon material is coated on Si oxide and metallic copper.Since Si oxide has cavernous structure,
Metallic copper is coated on the surface and hole wall of Si oxide.Metallic copper is added in negative electrode material, and Si oxide not only can be improved
Electric conductivity, be conducive to charge fast transfer in negative electrode material, but also can be reduced the agglomeration of nanometer Si oxide,
Guarantee there is electrical contact between nanometer Si oxide, makes negative electrode material that there is stable chemical property.In addition, being coated on metal
The carbon material of the Si oxide of copper clad not only can be further improved the electric conductivity of negative electrode material, but also for cathode material
Expect the bulk effect in charge and discharge process, provide good buffer function, makes negative electrode material that there is stable cycle performance.
The present invention also provides a kind of negative electrode material, negative electrode material includes Si oxide SiOx, graphene and unordered carbon materials
Material, wherein 1≤x≤2.The specific gravity range that graphene accounts for negative electrode material is 0.5-20%.Unordered carbon material is coated on Si oxide
SiOxAnd graphene, specifically, the form of unordered carbon material includes but are not limited to film or particle.
Graphene has heating conduction outstanding and mechanical property, and theoretical specific surface area is up to 2600m2/ g is high at room temperature
The electron mobility of speed, graphene can not only reduce the agglomeration of nanometer Si oxide, guarantee between nanometer Si oxide
There are electrical contacts, and the electric conductivity of Si oxide can be improved.In addition to this, be coated in negative electrode material Si oxide and
While unordered carbon material on graphene further increases the electric conductivity of negative electrode material, for negative electrode material in charge and discharge
Bulk effect in journey provides good buffer function, and negative electrode material is made to have stable cycle performance.
The negative electrode material with cladding form provided by the invention has apparent in the bulk effect of silicon based anode material
Improve, further, is compounded with the negative electrode material of Ni metal or graphene, electric conductivity tool is greatly improved, and negative electrode material exists
While with higher capacity, also there is highly stable cycle performance.
The present invention also provides a kind of preparation method of negative electrode material, preparation method includes the following steps:
Carbon material precursor is dissolved in the first solvent, Si oxide is added into the first solvent dissolved with carbon material precursor
SiOx, the second solvent is added after mixing, the Si oxide SiO for coating carbon material precursorxPrecipitating, precipitated product drying is laggard
Row high-temperature process obtains the Si oxide SiO of carbon material claddingx, wherein 1≤x≤2.
First solvent disperses carbon material precursor sufficiently, uniformly, the first solvent is selected from two for dissolving carbon material precursor
One of methylformamide, dimethyl sulfoxide, sulfolane or N-Methyl pyrrolidone.
Specifically, being dissolved with the first solvent and Si oxide SiO of carbon material precursorxBall milling mixing is mixed into, when ball milling
The range of speeds be 100-900rpm, the time range of ball milling mixing is 5-45h.When ball milling, zirconium dioxide is used in ball grinder
Ball is ground, and in order not to destroy ball grinder, introduces impurity, and is fully ground Si oxide and evenly dispersed, excellent
The rotational speed of ball-mill of choosing is 300rpm.Ball milling can effectively disperse nano material, and Si oxide is made to be uniformly dispersed in carbon material
In precursor.
Second solvent includes one of water, methanol, ethyl alcohol, propyl alcohol, and the purpose that the second solvent is added is before making carbon material
The Si oxide SiO of body claddingxIt is precipitated out from the first solvent, and guarantees that Si oxide is uniformly dispersed in carbon material precursor
In.
The Si oxide SiO that precipitated product carbon material precursor is coatedxHigh-temperature process is carried out after drying, dry mode is not
Limit, it is therefore an objective to remove remaining solvent, the purpose of high-temperature process is that the pyrolysis of carbon material precursor is made to be carbon, obtains carbon material cladding
Si oxide SiOx, carbon material is coated on the surface or hole wall of Si oxide, obtains the negative electrode material of cladding form.
The purpose that precipitated product is carried out to high-temperature process after dry is to be pyrolyzed carbon material precursor for carbon, to be coated on silicon
The surface of oxide.Temperature range when high-temperature process is 600-1200 DEG C, and temperature is relatively low, and carbon material pyrolysis may be made not fill
Point, temperature is excessively high, it may occur that other side reactions；In order to make pyrolysis sufficiently, high-temperature process time range is 1-6h.
Carbon material precursor be selected from polyacrylonitrile, polypyrrole, polyvinyl chloride, Kynoar, polyvinyl alcohol, polystyrene,
At least one of phenolic resin, epoxy resin, coal tar asphalt, asphalt, sucrose or glucose.Carbon material precursor can be with
It is solid-state form, is also possible to dissolve liquid form in a solvent.
Further, the negative electrode material that high-temperature process obtains is dissolved into part Si oxide with hydrogen fluoride solution, into
One step improves the porosity of negative electrode material, obtains more porous negative electrode material, bulk effect when being negative electrode material charge and discharge
Bigger cushion space is provided.In order to achieve the purpose that only to dissolve the Si oxide of part, hydrogen fluoride solution is dilute hydrogen fluoride
Solution, specifically, the mass concentration range of hydrogen fluoride solution is 5-10%.
Homogeneous solution is formed specifically, polyacrylonitrile (PAN) is dissolved in N-Methyl pyrrolidone (NMP), by nanometer
SiO or SiO2Particle is dispersed in homogeneous solution, ball milling mixing 36h, and SiO or SiO that ethyl alcohol coats PAN is added2Precipitating, with
Precipitated product is dried in vacuo removal NMP afterwards, carries out high-temperature process at protective gas, 1000 DEG C, making PAN pyrolysis is carbon, is obtained
Obtain the Si oxide of carbon material cladding.
The present invention also provides a kind of preparation method of negative electrode material, preparation method includes the following steps:
Carbon material precursor is dissolved in the first solvent, Si oxide is added into the first solvent dissolved with carbon material precursor
SiOxAnd graphene, the second solvent is added after mixing, the Si oxide SiO for coating carbon material precursorxIt is precipitated with graphene, it will
High-temperature process is carried out after precipitated product is dry, obtains the Si oxide SiO of unordered carbon material claddingxAnd graphene, wherein 1≤x
≤2。
First solvent disperses carbon material precursor sufficiently, uniformly, the first solvent is selected from two for dissolving carbon material precursor
One of methylformamide, dimethyl sulfoxide, sulfolane or N-Methyl pyrrolidone.
Specifically, being dissolved with the first solvent, the Si oxide SiO of carbon material precursorxIt is mixed into ball milling mixing with graphene,
Range of speeds when ball milling is 100-900rpm, and mixed time range is 5-45h.When ball milling, titanium dioxide is used in ball grinder
The grinding of zirconium ball introduces impurity in order not to destroy ball grinder, and is fully ground Si oxide and evenly dispersed, preferably
Rotational speed of ball-mill be 300rpm.
Second solvent includes one of water, methanol, ethyl alcohol, propyl alcohol, and the purpose that the second solvent is added is before making carbon material
The Si oxide SiO of body claddingxIt is precipitated out from the first solvent with graphene, and guarantees Si oxide and graphene uniform
It is dispersed in carbon material precursor.
The Si oxide SiO that precipitated product carbon material precursor is coatedxHigh-temperature process is carried out with after graphene drying, it is dry
Mode it is unlimited, it is therefore an objective to remove remaining solvent, the purpose of high-temperature process is that the pyrolysis of carbon material precursor is made to be carbon, makes carbon material
It is coated on Si oxide SiOxAnd graphene, obtain the negative electrode material of cladding form.
The purpose that precipitated product is carried out to high-temperature process after dry is to be pyrolyzed carbon material precursor for disordered carbon, to coat
In the surface of Si oxide and graphene, temperature range when high-temperature process is 600-1200 DEG C, and temperature is relatively low, may make carbon
Materials pyrolysis is insufficient, and temperature is excessively high, it may occur that other side reactions；In order to make pyrolysis, sufficiently high-temperature process time range is
1-6h。
Carbon material precursor be selected from polyacrylonitrile, polypyrrole, polyvinyl chloride, Kynoar, polyvinyl alcohol, polystyrene,
At least one of phenolic resin, epoxy resin, coal tar asphalt, asphalt, sucrose or glucose.Carbon material precursor can be with
It is solid-state form, is also possible to dissolve liquid form in a solvent.
Likewise, the negative electrode material that high-temperature process obtains is dissolved part Si oxide with hydrogen fluoride solution, further
Improve negative electrode material porosity, obtain porous negative electrode material, be negative electrode material charge and discharge when bulk effect provide more greatly
Cushion space.In order to achieve the purpose that only to dissolve the Si oxide of part, hydrogen fluoride solution is dilute hydrogen fluoride solution, specifically
, the mass concentration range of hydrogen fluoride solution is 5-10%.
Homogeneous solution is formed specifically, PAN is dissolved in NMP, by Nano-meter SiO_2 or SiO2Particle, graphene dispersion exist
In homogeneous solution, SiO or SiO that ethyl alcohol coats PAN is added in ball milling mixing 36h2Particle and graphene precipitating, will then sink
The dry removal NMP of shallow lake product, carries out high-temperature process at protective gas, 1000 DEG C, and making PAN pyrolysis is disordered carbon, obtains unordered
The Si oxide and graphene of carbon material cladding.Finally, the dilute fluorination of Si oxide and graphene that unordered carbon material is coated
Hydrogen solution dissolves part SiO or SiO2, to obtain porous negative electrode material.
Preparation method provided by the invention prepares negative electrode material in conjunction with mechanical ball mill and pyrolysis, largely mentions
The high degree of scatter of Si oxide or Si oxide and graphene in carbon material, and the cathode material with cladding form is made
Material.Negative electrode material has porous structure, can provide sufficient cushion space for bulk effect in charge and discharge, and be compounded with
The negative electrode material of graphene has clear improvement on electric conductivity.Preparation method is simple in the present invention, is prepared
Negative electrode material has excellent chemical property.
The present invention also provides a kind of preparation method of negative electrode material, preparation method includes the following steps:
By Si oxide SiOxIt is dispersed in copper nitrate solution, the solvent in dry removal solution, by the silicon oxygen after drying
Compound SiOx1-4h is handled at 170-300 DEG C of temperature with copper nitrate, obtains the Si oxide of oxidation copper clad, wherein 1≤x
≤2；
Carbon material precursor is dissolved in the first solvent, oxidation copper-clad is added into the first solvent dissolved with carbon material precursor
The Si oxide SiO coveredx, the second solvent is added after mixing, the Si oxide SiO for the oxidation copper clad for coating carbon material precursorx
Precipitating will carry out high-temperature process after precipitated product drying, be pyrolyzed carbon material precursor, copper oxide is reduced into copper, makes carbon material packet
The Si oxide SiO for the copper clad coveredx。
Specifically, when the Si oxide of preparation oxidation copper clad, with SiO2For, copper nitrate is dissolved in deionized water
In, it continuously stirs, by nanometer silicon oxide particles ultrasonic disperse in copper nitrate solution, SiO2Particle diameter range is 1-
100nm.Then, the water at 100 DEG C in dry removal copper nitrate solution.In order to make copper nitrate be completely decomposed into copper oxide and
Other side reactions will not be generated, dry gains are handled 1-4 hours at 170-300 DEG C in air environment, the oxygen of generation
Change copper clad in the Nano-meter SiO_2 with porous structure2On surface and hole wall, to improve Nano-meter SiO_22Electric conductivity, inhibit to receive
Rice SiO2Reunion, and even if a small amount of Nano-meter SiO_22Reunite, Nano-meter SiO_22Electrical contact is still remained between particle.
First solvent disperses carbon material precursor sufficiently, uniformly, the first solvent is selected from two for dissolving carbon material precursor
One of methylformamide, dimethyl sulfoxide, sulfolane or N-Methyl pyrrolidone.
Specifically, the Si oxide SiO of the first solvent, oxidation copper clad dissolved with carbon material precursorxIt is mixed into ball milling
Mixing, range of speeds when ball milling are 100-900rpm, and mixed time range is 5-45h.When ball milling, used in ball grinder
Zirconia balls grinding introduces impurity, and Si oxide is made to be fully ground and uniformly be divided in order not to destroy ball grinder
It dissipates, preferred rotational speed of ball-mill is 300rpm.
Second solvent includes one of water, methanol, ethyl alcohol, propyl alcohol, and the purpose that the second solvent is added is before making carbon material
The Si oxide SiO of the oxidation copper clad of body claddingxIt is precipitated out from the first solvent, and guarantees to aoxidize the silicon oxidation of copper clad
Object SiOxIt is uniformly dispersed in carbon material precursor.
By the Si oxide SiO of the oxidation copper clad of precipitated product carbon material precursor claddingxHigh-temperature process is carried out after drying,
Dry mode is unlimited, it is therefore an objective to remove remaining solvent, the purpose of high-temperature process is that the pyrolysis of carbon material precursor is made to be carbon, carbon into
One step reductive copper oxide is copper, and carbon material is made to be coated on the Si oxide SiO of copper cladx, obtain the negative electrode material of cladding form.
High-temperature process is carried out in protective gas atmosphere, and protective gas includes but are not limited to nitrogen, argon gas.
The purpose that precipitated product is carried out to high-temperature process after dry is to be pyrolyzed carbon material precursor for carbon, to be coated on silicon
The surface of oxide and metallic copper, temperature range when high-temperature process are 600-1200 DEG C, and temperature is relatively low, may make carbon material
It is pyrolyzed insufficient, temperature is excessively high, it may occur that other side reactions；In order to make pyrolysis sufficiently, high-temperature process time range is 1-6h.
Carbon material precursor be selected from polyacrylonitrile, polypyrrole, polyvinyl chloride, Kynoar, polyvinyl alcohol, polystyrene,
At least one of phenolic resin, epoxy resin, coal tar asphalt, asphalt, sucrose or glucose.Carbon material precursor can be with
It is solid-state form, is also possible to dissolve liquid form in a solvent.
Further, the negative electrode material that high-temperature process obtains is dissolved into part Si oxide with dilute hydrogen fluoride solution,
The voidage for further increasing negative electrode material obtains porous negative electrode material, and bulk effect when being negative electrode material charge and discharge mentions
For bigger cushion space.
Homogeneous solution is formed specifically, polyacrylonitrile is dissolved in N-Methyl pyrrolidone (NMP), copper clad will be aoxidized
Si oxide be dispersed in homogeneous solution, ball milling mixing 36h, be added ethyl alcohol make polyacrylonitrile coat oxidation copper clad silicon
Oxide precipitation carries out high-temperature process, preferably then by the dry removal NMP of precipitated product at protective gas, 500-1200 DEG C
, temperature range is 600-1200 DEG C, and making PAN pyrolysis is carbon, obtains the Si oxide of the copper clad of carbon material cladding.
Finally, the Si oxide of the copper clad of carbon material cladding is dissolved into part Si oxide with hydrogen fluoride solution, from
And obtain porous negative electrode material.In order to achieve the purpose that only to dissolve the Si oxide of part, hydrogen fluoride solution is dilute fluorination
Hydrogen solution, specifically, the mass concentration range of hydrogen fluoride solution is 5-10%.
Preparation method provided by the invention prepares negative electrode material in conjunction with mechanical ball mill and the precipitation method, largely
Si oxide is improved in the degree of scatter of carbon material precursor.Ball milling, the Si oxide that copper oxide can be made to coat is effective, fills
That divides is dispersed in carbon material precursor, specifically, forming the silicon oxidation of evenly dispersed oxidation copper clad in PAN solution
Object.Ethyl alcohol is added into mixed solution, the Si oxide of PAN/ oxidation copper clad can be made to be settled out from nmp solvent rapidly
Come, obtains the Si oxide of PAN/ oxidation copper clad, PAN is evenly coated at the silicon oxide surface of oxidation copper clad, to protect
The Si oxide of oxidation copper clad is generally evenly distributed in PAN when demonstrate,proving high-temperature process, to prevent the electrode in cyclic process
Microstructure local failure.Preparation method is simple in the present invention, and the negative electrode material being prepared has excellent electricity
Chemical property.
Present invention further teaches a kind of cathode, cathode includes negative electrode material as described above.
Well known to those skilled in the art, cathode generally includes negative current collector and negative electrode material.Negative current collector is to be used for
Effective collection, which results from the electric current of cathode and provides effective electric interface, is led to external circuit for electric current.Negative current collector
Material can be selected from material appropriate based on the present invention, for example, negative current collector may include but be not limited only to foam copper
Or nickel foam.
When preparing cathode, conductive agent and binder can also be added as needed in negative electrode material.
Conductive agent be selected from conducting polymer, active carbon, graphene, carbon black, carbon fiber, metallic fiber, metal powder and
One of sheet metal is a variety of.Specifically, conductive agent is selected from acetylene black (AB).
Binder is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination
Polymer, carboxymethyl cellulose, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, polyethylene glycol dimethyl allene
The mixture and derivative of one of acid or above-mentioned polymer.Specifically, binder is selected from carboxymethyl cellulose (CMC).
Present invention further teaches a kind of battery, battery includes anode, cathode and the electrolysis between anode and cathode
Liquid.Cathode includes negative electrode material as described above.
Anode includes plus plate current-collecting body and positive electrode active materials.Wherein, plus plate current-collecting body may include but be not limited only to aluminium.
Those skilled in the art are it is recognised that the material of plus plate current-collecting body can be metallic nickel or other metals.In order to increase and anode
The material of the contact of active material, plus plate current-collecting body can also select the aluminium with carbon coating.Compared with simple aluminium collector,
The aluminium collector of carbon coating has good adhesion properties, lower contact resistance.Specifically, carbon coating nanometer can also be selected
The aluminium of pipe array.In addition to this, plus plate current-collecting body can also be carbon-based material or alloy.
Positive electrode active materials participate in electrochemical reaction, including can it is reversible deviate from-material of embedded ion or functional group.
Specifically, positive electrode active materials include can it is reversible deviate from-be embedded in lithium ion, sodium ion, zinc ion or magnesium from
The material of son.Wherein, can it is reversible deviate from-material that is embedded in lithium ion includes but are not limited to spinel structure or stratiform
The material of structure or olivine structural.
At present in Lithium Battery Industry, nearly all positive electrode active materials all can be through modifications such as overdoping, claddings.But it mixes
Miscellaneous, the means such as coating modification cause the chemical general formula of material to express complicated, such as LiMn2O4Can not represent makes extensively at present
The general formula of " LiMn2O4 ", and being construed as widely includes the LiMn by various modifications2O4Positive electrode active materials.Together
Sample, LiFePO4And LiCoO2Also it should be construed broadly to include by modified positive-actives such as various doping, claddings
Material.
When positive electrode active materials of the invention are lithium ion abjection-inlaid scheme, it can select such as LiMn2O4、
LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).In addition, can deviate from-be embedded in
The compound of sodium ion such as NaVPO4F can deviate from-be embedded in the compound such as λ-MnO of zinc ion2, can deviate from-it is embedded in magnesium ion
Compound such as MgMxOy(wherein M be a kind of metal, 0.5 < x < 3,2 < y < 6) and have similar functions, can deviate from-be embedded in from
Son or the compound of functional group all can serve as the positive electrode active materials of battery of the present invention.
Further, positive electrode active materials contain sulfenyl material, and sulfenyl material is selected from elementary sulfur, Li2Sn, organic sulfur compound
With carbon-sulfur polymer (C2Sv)mAt least one of, wherein n >=1,2.5≤v≤50, m >=2.Sulfenyl material accounts for positive-active material
Expect the 70-90% of total weight.Preferably, the weight proportion of the sulfenyl material in positive electrode active materials is 80%.
When preparing positive electrode active materials, conductive agent and binder can also be added as needed.
Conductive agent be selected from conducting polymer, active carbon, graphene, carbon black, carbon fiber, metallic fiber, metal powder and
One of sheet metal is a variety of.Specifically, conductive agent includes section's qin carbon black (KB).
Binder is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination
One of polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates or
The mixture and derivative of above-mentioned polymer.In a specific embodiment, binder includes polytetrafluoroethylene (PTFE) (PTFE)；Specifically
, binder includes Kynoar (PVDF).
In order to guarantee in charge and discharge process, between the positive electrode and negative electrode of battery exist can it is reversible deviate from-be embedded in from
Son, such as: lithium ion when the sulfenyl material and silica-base material of selection are free of lithium ion simultaneously, carries out anode and/or cathode pre-
Embedding lithium processing.The mode of specific pre- embedding lithium is unlimited, including the embedding lithium of chemical reaction or the embedding lithium of electrochemical reaction.
Electrolyte includes at least electrolyte lithium salt and mixed organic solvents.Electrolyte includes anodolyte and catholyte
Matter.
Electrolyte lithium salt includes but are not limited to lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4) or perchloric acid
Lithium (LiClO4).It will be recognized by those skilled in the art that lithium salts can effectively increase the ionic conductivity of electrolyte.
The mixed organic solvents of electrolyte can be common organic aqueous solution, such as dimethoxy-ethane (DME), second
Alkene carbonic ether (EC), carbovinate rouge (DEC), propylene carbonate (PC), 1,3- dioxolane (DIOX), various ether are sweet
Diethylene glycol dimethyl ether, lactone, sulfone, sulfolane or the above mixture.For example use 1,3- dioxolane (DIOX).It is also possible to polymerize
Object, such as polyacrylonitrile.It can also include gel, such as gelatin polymer (PEGMEMA1100-BMI).If using this electricity of gel
Certain deformation can occur for Xie Zhi, therefore the manufacture craft of corresponding battery will not be sent out since itself is a kind of soft material
Raw too big variation.It is of course also possible to use solid polymer electrolyte, such as Li2S-P2S5Glass-ceramic or P (EO)20Li
(CF3SO2)2N-10wt.% γ-LiAlO2。
Electrolyte in the battery, is conducive to prevent the leakage of potential battery electrolyte, avoided with the prominent form of gel
It pollutes the environment, while also improving the safety of battery.
The battery that a specific embodiment of the invention provides, if needed in battery structure using diaphragm, diaphragm is organic
Porous material or glass fiber material, the pore diameter range of diaphragm are 0.001 to 100 micron, and porosity ranges are 20 to 95%.
The form of battery includes but are not limited to the tabletting structure in microbattery applications, also include common button cell,
Cylindrical battery or plate-type battery.
Battery provided by the invention has excellent cycle performance, and battery cathode uses the cathode material with cladding form
Material, negative electrode material include at least the outer layer of internal layer and carbon material with Si oxide, and further, negative electrode material further includes
The electric conductivity of negative electrode material has can be improved in metallic copper or graphene, metallic copper or graphene, is conducive to charge fast transfer,
The silicon oxide particles of nano-scale can substantially reduce volume change when lithium ion insertion and abjection, meanwhile, it discharges for the first time
The Li generated in the process2O and lithium metasilicate are inertial base, can support and disperse active Si main body, are born in charge and discharge process
Volume change when lithium ion abjection and insertion；Have good positioned in outermost carbon material for big volume change
Buffer function, meanwhile, the porous structure of negative electrode material is the space that the volume change of Si oxide provides in the process, improves and contains
There is bulk effect when silicon based anode material, ensure that the cycle performance of negative electrode material.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
The PAN of 2.17g is dissolved in the NMP of 12mL and forms uniform solution, the SiO of 0.8g2It is mixed with PAN solution,
Mixture is 5 using diameter with revolving speed 300rpm, mechanical ball mill 36h by high energy ball mill (Pulverisette7, Germany)
The zirconia balls of millimeter, zirconia balls and mixture weight ratio are 10:1.After ball milling, ethyl alcohol is added into solution, makes PAN
The SiO of cladding2Precipitating.The SiO of PAN cladding2At 1000 DEG C, ultra-high purity nitrogen gas is protected lower high-temperature process 3 hours, makes PAN heat
Solution is carbon, heating rate 10K/min, gas flow rate 100mL/min.
Fig. 1 is the negative electrode material SiO that embodiment 1 provides2The X ray diffracting spectrum of/C.As can be seen from the figure SiO2And C
It is amorphous.
Fig. 2 is the negative electrode material SiO that embodiment 1 provides2The thermogravimetric analysis (TG) of/C and differential thermal analysis (DTA) curve,
The result shows that SiO in negative electrode material2It respectively may be about 40% and 60% with C content.
Embodiment 2
The PAN of 1.62g is dissolved in the NMP of 10mL and forms uniform solution.SiO the and PAN solution of 0.6g is in bottle
Mixing, mixture, with revolving speed 300rpm, mechanical ball mill 36h, use two that diameter is 5 millimeters by high energy ball mill mechanical ball mill
Zirconia ball, zirconia balls and mixture weight ratio are 10:1.After ball milling, ethyl alcohol is added into solution, coats PAN
SiO precipitating.The SiO of PAN cladding is at 1000 DEG C, and ultra-high purity nitrogen gas is protected lower high-temperature process 3 hours, and making PAN pyrolysis is carbon,
Heating rate is 10K/min, gas flow rate 100mL/min.Then, in order to provide enough spaces to the volume expansion of SiO,
Part SiO then is dissolved with 5% dilute hydrogen fluoride solution, obtaining has more porous negative electrode material.
Fig. 3 is scanning electron microscope (SEM) picture for the negative electrode material SiO/C that embodiment 2 provides.It can from figure
SiO particle is coated by C out.
Embodiment 3
By 0.96g copper nitrate (Cu (NO3)2·3H2O).Copper nitrate is to dissolve in deionized water, lasting to stir, 1g's
SiO2Porous ball (diameter 5-15nm) ultrasonic disperse is in copper nitrate solution.Then, water evaporation is contained at 100 DEG C
There are copper nitrate and SiO2Solid mixture, solid mixture handles 3 hours at 300 DEG C in air environment, makes copper nitrate point
Solution becomes copper oxide (CuO), forms the Nano-meter SiO_2 of CuO cladding2。
The PAN of 1.30g is dissolved in 10mL NMP and forms uniform solution, the SiO of 0.8g CuO cladding2It is molten with PAN
Liquid mixing, resulting mixture is by high energy ball mill (Pulverisette7, Germany) with revolving speed 300rpm mechanical ball mill
36h, the zirconia balls for the use of diameter being 5 millimeters, zirconia balls and mixture weight ratio are 10:1.To the solution after ball milling
Middle addition ethyl alcohol, the SiO for the CuO cladding for coating PAN2Precipitating.It is carbon to make polyacrylonitrile-radical pyrolysis, and by copper oxide
It is reduced into copper, by negative electrode material at 1000 DEG C, high-temperature process 3 hours under ultra-high purity nitrogen gas protection, heating rate 10
K/min, gas flow rate 100mL/min.
Fig. 4 is the negative electrode material SiO that embodiment 3 provides2The X-ray diffractogram of/Cu/C.As can be seen from the figure: cathode
Material is by SiO2, Cu and C are formed.And during heat treatment, copper oxide is successfully reduced into crystalline state copper by C, and C is without fixed
Shape.
Fig. 5 is the negative electrode material SiO that embodiment 3 provides2The TG and DTA curve of/Cu/C, as seen from the figure: a part of C quilt
Cu is surrounded, and compared with the C not coated by Cu, it needs higher ignition temperature, because the CuO's being thermally formed in air leads
It is hot poor.SiO2, Cu, C content be respectively 40%, 7% and 53%.
Embodiment 4
The PAN of 1.3g is dissolved in the NMP of 12mL and forms uniform solution, the graphene of SiO, 0.12g of 0.6g and
The mixing of PAN solution, mixture is by high energy ball mill with revolving speed 300rpm, mechanical ball mill 36h.After ball milling, it is added into solution
Ethyl alcohol, the SiO for coating PAN and graphene precipitating.The SiO and graphene of PAN cladding are at 1000 DEG C, ultra-high purity nitrogen gas
It protects lower the high temperature anneal 3 hours, making PAN pyrolysis is C, heating rate 10K/min, gas flow rate 100mL/min.
The SiO and graphene of C cladding are obtained finally by ball milling.
Fig. 6 is the SiO for the negative electrode material C cladding that embodiment 4 provides and the SEM picture of graphene.As can be seen from the figure
SiO particle and graphene are by carbon coating.
2032 type button cells are assembled in the glove box full of argon gas to study the chemical property of negative electrode material.
Embodiment 5
According to weight ratio 80:5:15, by negative electrode material SiO/C, acetylene black (AB) and carboxymethyl cellulose (CMC) mixing,
It takes water as a solvent and slurry is made, slurry is coated in nickel foam, the film of formation is dried in vacuo 12 hours at 100 DEG C,
Working electrode is made.Lithium is used as to electrode, and electrolyte is to contain 1M LiPF6Ethylene carbonate (EC), dimethyl carbonate
(DMC) mixed solvent of (weight 1:1), wherein the vinylene carbonate (VC) of addition 2%.Diaphragm be microporous polypropylene membrane (PP,
Celgard2400).Charge and discharge are carried out to battery using different constant current densities, the voltage range of battery is 0-2.0V.Every time
Charge and discharge cycles interval 1 minute.
Fig. 7 is the battery that provides of embodiment 5 with constant current density 100mA/g charge and discharge, cell voltage and specific capacity
Relation curve.Specific discharge capacity and charge specific capacity are respectively 1125 and 748mAh/g when battery recycles for the first time, are higher than carbon substrate
Material.Recycling secondary specific discharge capacity is 731mAh/g.
Fig. 8 is the battery of the offer of embodiment 5 with constant current density 100mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.Battery shows excellent cycle performance, in charge and discharge cycles
Battery discharge specific capacity becomes stable after 10 times, is 600mAh/g.Capacity retention ratio after circulating battery 100 times is higher than 85%,
Coulombic efficiency is almost 100%, shows that the cycle performance of battery is highly stable.
Fig. 9 be the battery that provides of embodiment 5 with different current density charge and discharge, specific discharge capacity and cycle-index and
Relation curve between coulombic efficiency and cycle-index.It can be seen from the figure that when charging and discharging currents density increases from 100mA/g
When to 200mA/g, 300mA/g, corresponding battery discharge specific capacity successively declines, and when charging and discharging currents density is restored to
When 100mA/g, battery discharge specific capacity can be restored to original level, show that high current charge-discharge will not make battery performance itself
At irreversible loss, in addition, battery, in different current density charge and discharge, battery coulombic efficiency is highly stable, approach
100%.
Embodiment 6
In embodiment 6, Si oxide SiO in negative electrode material2Substitute SiO, remaining material preparation process and battery composition
With embodiment 5.Battery voltage range is 0-3.0V.
Figure 10 is the battery of the offer of embodiment 6 with constant current density 55mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.Specific discharge capacity and coulombic efficiency point when battery recycles for the first time
It Wei not 782mAh/g and 51.4%.
Figure 11 is the battery that provides of embodiment 6 with constant current density 110mA/g charge and discharge, cell voltage and specific capacity it
Between relation curve.Battery first discharge specific capacity reaches 630mAh/g, and recycling secondary specific discharge capacity is 350mAh/g.
Embodiment 6 wants small compared to battery capacity in embodiment 5, shows negative electrode material using SiO2Instead of SiO, battery capacity is
It reduces.
Figure 12 is the battery of the offer of embodiment 6 with constant current density 110mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.Although the battery in embodiment 6 also shows good circulation
Performance, but its specific capacity decreased significantly with respect to the battery in embodiment 5.The result shows that the performance of the battery containing SiO wants bright
It is aobvious to be better than containing SiO2Battery.
Embodiment 7
In embodiment 7, negative electrode material uses the SiO and graphene of C cladding, remaining battery composition and test method with implementation
Example 5.
Figure 13 is that the battery that embodiment 7 provides carries out charge and discharge, specific discharge capacity to battery with constant current density 100mA/g
Relation curve between cycle-index and coulombic efficiency and cycle-index.As can be seen from the figure: battery has excellent
Cycle performance, after charge and discharge cycles 10 times, specific discharge capacity starts to stablize, about 700mAh/g, after charge and discharge cycles 100 times
Specific discharge capacity be 600mAh/g, capacity retention ratio be higher than 85%, coulombic efficiency contains in embodiment 5 close to 100%
Specific discharge capacity of the SiO/C battery when recycling 100 times is 510mAh/g, shows further to add graphene in negative electrode material,
The utilization rate of Si oxide in negative electrode material can be significantly improved, to improve battery performance.
Figure 14 be embodiment 7 provide battery with different current density charge and discharge, specific discharge capacity and cycle-index with
And the relation curve between coulombic efficiency and cycle-index.It can be seen from the figure that when charging and discharging currents density increases from 100mA/g
When being added to 200mA/g, 300mA/g, corresponding battery discharge specific capacity successively declines, and works as charging and discharging currents density from 300mA/
G, when 200mA/g is restored to 100mA/g, battery discharge specific capacity correspondence can be restored to original level, show high current charge-discharge
Irreversible loss is not will cause to battery performance itself, in addition, battery, in different current density charge and discharge, battery coulomb is imitated
Rate is highly stable, close to 100%.Compared to embodiment 5, the battery that embodiment 7 provides has higher specific capacity, shows cathode
Graphene is further added in material, can significantly improve the utilization rate of Si oxide in negative electrode material, to improve cell performance
Energy.
Embodiment 8
In embodiment 8, Si oxide SiO in negative electrode material2Instead of SiO, negative electrode material is the SiO of C cladding2And graphite
The weight ratio of alkene, AB and CMC are 85:5:10, remaining material preparation process and battery composition are the same as embodiment 5.
Figure 15 is the battery that provides of embodiment 8 with constant current density 55mA/g charge and discharge, cell voltage and specific capacity it
Between relation curve.Battery first discharge specific capacity is 550mAh/g, recycles secondary specific discharge capacity and slightly improves, is
580mAh/g。
Figure 16 is the battery of the offer of embodiment 8 with constant current density 55mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.After charge and discharge cycles 30 times, specific discharge capacity is about battery
450mAh/g, coulombic efficiency contain SiO in embodiment 6 close to 95%2/ C battery recycle 30 times when specific discharge capacity be
400mAh/g is further demonstrated and is further added graphene in negative electrode material, can be significantly improved silicon in negative electrode material and be aoxidized
The utilization rate of object, to improve battery performance.In addition, battery capacity is significantly lower than battery capacity in embodiment 7 in embodiment 8,
Also illustrate that the chemical property of SiO will be substantially better than SiO2。
Embodiment 9
According to weight ratio 80:5:15, by negative electrode material SiO2/ Cu/C, AB and CMC mixing, take water as a solvent and slurry are made,
Slurry is coated in nickel foam, working electrode is made.The film of formation is dried in vacuo 12 hours at 100 DEG C, lithium conduct pair
Electrode, electrolyte are to contain 1M LiPF6Ethylene carbonate (EC), dimethyl carbonate (DMC) (weight 1:1), 2% VC's
Mixed solvent.Diaphragm is microporous polypropylene membrane (PP, Celgard2400).The voltage range of battery is 0-3.0V, using different
Constant current density carries out charge and discharge to battery, is spaced 1 minute between each charge and discharge cycles.
Figure 17 is the battery that provides of embodiment 9 with constant current density 55mA/g charge and discharge, cell voltage and specific capacity
Relation curve.As can be seen from the figure: electric discharge and charge specific capacity when battery recycles for the first time be respectively 902mAh/g and
651mAh/g is higher than battery capacity for the first time in embodiment 8.In second of circulation, specific discharge capacity 653mAh/g, coulomb effect
Rate is increased to 96.3% from 72.2% for the first time.
Figure 18 is the battery of the offer of embodiment 9 with constant current density 55mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.It can be seen from the figure that battery has good cycle performance,
After charge and discharge cycles 10 times, specific discharge capacity tends towards stability, about 537mAh/g, and the capacity retention ratio after circulation 115 times is
100%.
Figure 19 is the battery of the offer of embodiment 9 with constant current density 110mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.Battery in embodiment 9 is same in high current density charge and discharge
Sample shows excellent cycle performance and higher specific discharge capacity.Reversible specific capacity when battery charging and discharging recycles 200 times is still
So up to 423mAh/g.
Comparative example 1
According to weight ratio 50:20:30, by SiO2, AB and CMC are mixed, are taken water as a solvent and slurry is made, slurry is coated to
Working electrode is made in nickel foam.The electrochemical measurement of remaining battery composition is the same as embodiment 7.
Figure 20 is the battery of the offer of comparative example 1 with constant current density 55mA/g charge and discharge, specific discharge capacity and circulation time
The several and relation curve between coulombic efficiency and cycle-index.The specific capacity of pure silica electrode is only 45mAh/g, this
It may be related with conductive material AB.In addition, its coulombic efficiency is highly unstable.This result shows that, pure silica pair
The electro-chemical activity of lithium is very low, works as SiO2It is only simply mixed with carbon, leads to carbon and SiO2Between interfacial contact it is very poor and
SiO2Lower electric conductivity.This also indicates that, SiO2Surface cladding C is very important.
Although detailed elaboration and citing have been done to technical solution of the present invention above, for those skilled in the art
For member, on the basis of not departing from essence of the present invention, above-described embodiment is modified and/or flexible or use is similar
Alternative solution, also within the scope of the present invention.
Claims (11)
1. a kind of negative electrode material, the negative electrode material includes Si oxide SiOxAnd carbon material, wherein 1≤x≤2, feature exist
In: the negative electrode material further includes metallic copper, and the specific gravity range that the metallic copper accounts for the negative electrode material is 0.5~30%, institute
It states metallic copper and is coated on the Si oxide SiOx, the carbon material is coated on the Si oxide SiOxAnd metallic copper.
2. negative electrode material according to claim 1, it is characterised in that: at least partly described Si oxide SiOxFor with hole
The nano particle of shape structure.
3. negative electrode material according to claim 1, it is characterised in that: the Si oxide SiOxAccount for the negative electrode material
Specific gravity range is 5~70%, and the specific gravity range that the carbon material accounts for the negative electrode material is 30~95%.
4. negative electrode material according to claim 1, it is characterised in that: the carbon material includes graphene and disordered carbon.
5. negative electrode material according to claim 4, it is characterised in that: the graphene accounts for the specific gravity model of the negative electrode material
Enclose is 0.5~20%.
6. negative electrode material according to claim 4, it is characterised in that: the disordered carbon is coated on the Si oxide SiOx
And graphene.
7. negative electrode material according to claim 1, it is characterised in that: the Si oxide SiOxFor Nano-meter SiO_22；It is described negative
The grain shape of pole material is spherical.
8. negative electrode material according to claim 7, it is characterised in that: described on the basis of the quality of the negative electrode material
Nano-meter SiO_2 described in negative electrode material2Mass percentage be 40%~60%.
9. negative electrode material according to claim 1, it is characterised in that: the Si oxide SiOxFor SiO1.5, the carbon materials
Material is graphene.
10. a kind of cathode, it is characterised in that: the cathode includes such as cathode material any one of in claim 1~9
Material.
11. a kind of battery, including anode, cathode and the electrolyte between anode and cathode, it is characterised in that: described negative
Pole includes such as negative electrode material any one of in claim 1~9.
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| CN111146422A (en) * | 2019-12-26 | 2020-05-12 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
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| CN103872327B (en) * | 2014-04-04 | 2016-05-11 | 西华师范大学 | Preparation method and negative pole and the lithium ion battery of anode material for lithium battery |
| WO2015182123A1 (en) * | 2014-05-29 | 2015-12-03 | 株式会社豊田自動織機 | Silicon material and secondary cell negative electrode |
| KR102276423B1 (en) * | 2014-06-10 | 2021-07-12 | 삼성전자주식회사 | Composite, electrochemical active material composite using the composite, electrode including the same, lithium battery including the same, electroluminescent device including the same, biosensor including the same, semiconductor device including the same, and thermoelectric device including the same |
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| WO2014032595A1 (en) | 2014-03-06 |
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