CN109659486A - Preparation method, cathode and the lithium ion battery of negative electrode of lithium ion battery - Google Patents
Preparation method, cathode and the lithium ion battery of negative electrode of lithium ion battery Download PDFInfo
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- CN109659486A CN109659486A CN201811401891.6A CN201811401891A CN109659486A CN 109659486 A CN109659486 A CN 109659486A CN 201811401891 A CN201811401891 A CN 201811401891A CN 109659486 A CN109659486 A CN 109659486A
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
This application discloses a kind of preparation method of negative electrode of lithium ion battery, cathode and lithium ion batteries, the preparation method of negative electrode of lithium ion battery mixes the following steps are included: dispersing porous silica material in solvent with carbon source, it is then coated on collector, and heating is pyrolyzed to get negative electrode of lithium ion battery is arrived in atmosphere of inert gases.The preparation method simple process of above-mentioned negative electrode of lithium ion battery, porous Si-C composite material no longer needs to be prepared by mixing into slurry with binder, conductive agent, but it is directly coated on collector and cathode is made, the destruction in prior art pulping process to composite material granular pattern is avoided, and energy density is high.
Description
Technical field
The present invention relates to lithium ion battery manufacturing field, in particular to a kind of preparation method of negative electrode of lithium ion battery is born
Pole and lithium ion battery.
Background technique
Silicon has high theoretical specific capacity (4200mAh/g, Li as one of lithium ion battery negative material4.4Si), than
10 times of existing market graphite electrode specific capacity (372mAh/g) are taller；De- lithium voltage platform (< 1V moderate simultaneously
Vs.Li+/Li) and silicon resource abundant is concerned it in negative electrode of lithium ion battery preparation field.But silicon is in charge and discharge
There are serious volume expansions in journey, lead to material granule dusting, fall off, it is difficult to form stable solid electrolyte film, make material
Material is easy to lose electrical contact with collector, and negative pole structure is destroyed, and material loses activity.Silicon presently, there are aiming at the problem that, must
The volume expansion of silicon must be reduced and silicon is avoided to contact with the direct of electrolyte, in order to improve the stability and electrochemistry of silicon
Energy.
When silicon particle is nano material, the smaller dusting for advantageously reducing particle of partial size；Specific surface area height makes electrode
Increase with the contact area of electrolyte, facilitates the insertion abjection of more lithium ions, improve Li+Transmission rate.But it is general
Nanometer silicon preparation method can not avoid the problem that completely material surface is oxidized；In addition it is difficult to when silicon nanoparticle materials'use point
It dissipates, reunite seriously, concurrently there are the problems such as individual particle internal resistance is big, conductivity is low.
The silicon of porous structure buffer volumes can expand in charge and discharge process, so that material be avoided to be destroyed, guarantee electricity
The cyclical stability of pole material.When coating one layer of carbon on the surface of silicon particle, composite material is formed, in the volume expansion of silicon
Play the role of buffering.However, there are in complex process, equipment valuableness and preparation process for the preparation of above-mentioned Si-C composite material
The problems such as using highly toxic raw material；It is all first meanwhile when using above-mentioned porous preparation of silicon carbon composite materials negative electrode of lithium ion battery
Composite material is prepared, then binder is added in the composite and conductive agent is prepared into slurry, slurry is coated in
Electrode slice is formed on collector.This preparation process complexity and long flow path, are easy to destroy composite wood during preparing slurry
The structure and pattern of material, to influence the performance of material；Proportion is about 5%~20% to binder in the electrodes simultaneously, is glued
The addition of knot agent can reduce the capacity of electrode, reduce the energy density of battery.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of negative electrode of lithium ion battery, cathode and lithium ion battery, with
Solve the preparation process of negative electrode of lithium ion battery and porous Si-C composite material complexity, long flow path, at high cost in the prior art
Technical problem.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
The present invention provides a kind of preparation methods of negative electrode of lithium ion battery, comprising the following steps: by porous silica material with
Carbon source, which is scattered in solvent, to be mixed, and is then coated on collector, and in atmosphere of inert gases heating pyrolysis to get to lithium from
Sub- battery cathode.
Further, the partial size of the porous silica material is 50nm~500nm, and aperture is 1nm~200nm, specific surface area
For 100m2/ g~280m2/g。
Further, the porous silica material and the mass ratio of the carbon source are 1: 0.01~1.2, and preferred mass ratio is 1:
0.5~1.2.
Further, the carbon source is selected from by polyacrylonitrile, Kynoar, polyvinyl alcohol, polyethylene glycol, Guar
Glue, polymethyl methacrylate, hydroxypropyl cellulose and polyethylene glycol oxide group are at least one of in groups.
Further, the solvent be selected from by n,N-Dimethylformamide, n,N-dimethylacetamide, deionized water,
Dehydrated alcohol, tetrahydrofuran, N-Methyl pyrrolidone and dimethyl sulfoxide group are at least one of in groups.
Further, the temperature of the pyrolysis is 300 DEG C~1000 DEG C, and the time of pyrolysis is 0.5h~12h, is preferably pyrolyzed
300 DEG C~800 DEG C of temperature, pyrolysis time 0.5h~5h, 300 DEG C~600 DEG C of more preferable pyrolysis temperature, pyrolysis time 0.5h~
3h。
Further, the collector is copper foil, nickel foil, carbon cloth, stainless (steel) wire or titanium foil.
Further, the porous silica material preparation method the following steps are included: by silica and metallic reducing agent,
Fused salt mixing, under inert gas protection, temperature reaction, reaction use acid soak to get the porous silicon is arrived after completing and cooling down
Material.
Further, the silica, metallic reducing agent, fused salt mass ratio be 1: 0.1~5: 1~30, preferably 1
: 0.2~2: 5~20.
Further, reaction temperature is 200 DEG C~1000 DEG C in the preparation process of the porous silica material, and the reaction time is
0.5h~12h；650 DEG C~750 DEG C of preferable reaction temperature, reaction time 1h~7h.
Further, the operation of the acid soak specifically: first be added concentration be 0.1mol/L~5mol/L hydrochloric acid or
Sulfuric acid removes impurity, adds the complete silica of the hydrofluoric acid removal unreacted of 0.3wt.%~5wt.%.
Further, the metallic reducing agent by selected from by lithium, sodium, potassium, magnesium and aluminium group at least one of in groups.
Further, the metallic reducing agent is powdered, and the partial size of metal powder is 100 mesh~1000 mesh, preferably
500 mesh~1000 mesh.
Further, the fused salt is selected from metal halide, preferably sodium chloride and/or potassium chloride.
Further, the preparation method of the silica is the following steps are included: alkyl silicate and dehydrated alcohol are mixed
After conjunction, ammonium hydroxide is added, adjusting pH value is 8~11, and reaction obtains silica.
Further, the alkyl silicate is ethyl orthosilicate, the body of the ethyl orthosilicate and the dehydrated alcohol
Product is than being 1~10: 20~200, preferably 1~5: 20~100.
Further, be additionally added template in the preparation method of the silica, the template be carbon ball, F127, F123,
Cetyl trimethylammonium bromide or polystyrene.
Further, further comprising the steps of: pecvd process in situ, the gas of ionization are carried out after the completion of heating pyrolysis step
Body is methane or acetylene.
The present invention also provides a kind of negative electrode of lithium ion battery, are prepared by the preparation method of above-mentioned negative electrode of lithium ion battery
It arrives.
The present invention also provides a kind of lithium ion battery, the lithium ion battery being prepared including above-mentioned preparation method is negative
Pole.
Compared with prior art, the invention has the following advantages:
1, the preparation method of negative electrode of lithium ion battery of the invention, is directly coated on after being mixed with porous silica material with carbon source
On collector, negative electrode of lithium ion battery can be obtained after pyrolysis.The method of the present invention simple process, porous Si-C composite material are not necessarily to
Slurry is prepared by mixing into binder, conductive agent again, but is directly coated on collector and cathode is made, avoids the prior art
To the destruction of composite material granular pattern in pulping process, and energy density is high.
2, porous Si-C composite material obtained in preparation process of the present invention, after silicon and carbon source including porous structure are pyrolyzed
What is generated takes into account mechanical strength and thermoplastic carbon, and carbon is present in inside the porous structure of porous silica material and particle surface, has
It conducive to the volume expansion for inhibiting silicon, is also beneficial to maintain particle contact between particle, particle and collector, to keep negative
The structural stability of pole；Meanwhile also substantially increasing material electric conductivity.
3, the present invention, which by carbon source be pyrolyzed the carbon material formed in situ and can effectively avoid the direct of silicon and electrolyte, contacts, and makes to answer
The side reaction of condensation material and electrolyte is few and compatibility is good, to inhibit destruction of the electrolyte to material, improves cyclical stability.
4, there is superior electrochemistry cycle performance and higher energy by lithium ion battery prepared by cathode of the invention
Metric density.
Detailed description of the invention
Fig. 1 is the flow diagram for the negative electrode of lithium ion battery preparation method that the preferred embodiment for the present invention provides；
Fig. 2 is the X-ray diffraction spectrum figure of porous silica material in the preferred embodiment of the present invention 5；
Fig. 3 is the graph of pore diameter distribution of porous silica material in the preferred embodiment of the present invention 5；
Fig. 4 is the scanning electron microscope (SEM) photograph for the negative electrode of lithium ion battery that the preferred embodiment of the present invention 5 provides；
Fig. 5 is the cycle performance curve for the negative electrode of lithium ion battery that the preferred embodiment of the present invention 5 provides.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.With reference to the accompanying drawing and specific embodiment the present invention is further described in more detail.
Referring to Fig.1, the preferred embodiment of the present invention provides a kind of preparation method of negative electrode of lithium ion battery, including with
Lower step: dispersing porous silica material in solvent with carbon source and mix, and is then coated on collector, and in atmosphere of inert gases
Middle heating is pyrolyzed to arrive negative electrode of lithium ion battery.
It, can be with after porous silica material is mixed in a solvent with carbon source in the preparation method of above-mentioned negative electrode of lithium ion battery
Directly be coated on collector, then so that carbon is formed in the inside and surface of porous silica material through heating pyrolysis, be made be coated with it is more
The cathode of hole Si-C composite material.This preparation method simple process, porous Si-C composite material no longer need to and binder, conductive agent
It is prepared by mixing into slurry, but is directly coated on collector and cathode is made, is avoided in prior art pulping process to compound
The destruction of material granule pattern, energy density is high, and silicon particle is evenly distributed on a current collector, and negative pole structure is stablized.
Porous Si-C composite material obtained in present embodiment, what silicon and carbon source including porous structure generated after being pyrolyzed
Mechanical strength and thermoplastic carbon are taken into account, carbon is present in inside the porous structure of porous silica material and particle surface, is conducive to press down
The volume expansion of silicon processed is also beneficial to maintain particle contact between particle, particle and collector, to keep the knot of cathode
Structure stability；Meanwhile also substantially increasing material electric conductivity.Preferably, the partial size of porous silica material is 50nm~500nm, hole
Diameter is 1nm~200nm, specific surface area 100m2/ g~280m2/g.The lithium ion that the porous silica material of above-mentioned specification is prepared
Battery cathode is conducive to the volume expansion for buffering silicon in charge and discharge process.Preferably, porous silica material and carbon source are with mass ratio
1: 0.01~1.2 mixing, it is highly preferred that porous silica material is mixed with carbon source with mass ratio 1: 0.5~1.2.Aforementioned proportion mixing
Porous silica material and carbon source fill uniformly with carbon material and coated porous silicon materials.Preferably, carbon source is selected from by poly- third
Alkene nitrile, Kynoar, polyvinyl alcohol, polyethylene glycol, guar gum, polymethyl methacrylate, hydroxypropyl cellulose and polyoxy
Change ethylene group at least one of in groups.The above-mentioned selection to porous silica material, carbon source and its mass ratio, after mixing the two
It is more easily directly coated on collector, is pyrolyzed obtained negative electrode of lithium ion battery and had excellent performance.
Present embodiment is pyrolyzed the carbon material formed by carbon source in situ can effectively avoid directly contacting for silicon and electrolyte, make
The side reaction of composite material and electrolyte is few and compatibility is good, to inhibit destruction of the electrolyte to material, improves stable circulation
Property.Preferably, the temperature that porous silica material is pyrolyzed after mixing and coat with carbon source is 300 DEG C~1000 DEG C, and pyrolysis time is
0.5h~12h, preferably 300 DEG C~800 DEG C of pyrolysis temperature, pyrolysis time 0.5h~5h, more preferable pyrolysis temperature 300 DEG C~600
DEG C, pyrolysis time 0.5h~3h.
In some embodiments, the preparation method of porous silica material is the following steps are included: silica and metal are restored
Agent, fused salt mixing, under inert gas protection, temperature reaction, reaction use acid soak to get porous silicon material is arrived after completing and cooling down
Material.Metallothermic reduction silica is utilized in above-mentioned the step of preparing porous silica material, is reused sour selective dissolution and is fallen metal
Oxide and/or metal are to obtain the porous silica material of self-supporting.The above-mentioned porous silica material being prepared is the silicon of pure phase.
Preferably, silica, metallic reducing agent, fused salt mass ratio be 1: 0.1~5: 1~30, be more preferably 1: 0.2~2: 5
~20.Preferably, reaction temperature be 200 DEG C~1000 DEG C, the reaction time be 0.5h~12h, 650 DEG C of preferable reaction temperature~
750 DEG C, reaction time 1h~7h.The operation of above-mentioned acid soak specifically: the salt that concentration is 0.1mol/L~5mol/L is first added
Acid or sulfuric acid remove impurity, add the complete silica of the hydrofluoric acid removal unreacted of 0.3wt.%~5wt.%.It is above-mentioned logical
The temperature and time that the material quality that preferably reacts is crossed than, reaction realizes silicon materials to regulate and control the production quantity of reduction intermediate product
The maximization of specific surface area, so that it is compound with carbon material to be conducive to it.
Preferably, in the preparation method of porous silica material metallic reducing agent by selected from being made of lithium, sodium, potassium, magnesium and aluminium
At least one of group.Above-mentioned metallic reducing agent be it is powdered, the partial size of metal powder is 100 mesh~1000 mesh, preferably 500
Mesh~1000 mesh.Preferably, fused salt is selected from metal halide, preferably sodium chloride and/or potassium chloride.Above-mentioned metallic reducing agent and molten
The selection of salt and requirement to metal powder partial size further guarantee the formation of the porous structure of porous silica material, thus
Be conducive to the filling and cladding of carbon material.
In some embodiments, the preparation method of silica is the following steps are included: by alkyl silicate and dehydrated alcohol
After mixing, ammonium hydroxide is added, adjusting pH value is 8~11, and reaction obtains silica.Using alkyl silicate and ethyl alcohol in alkaline item
Silica, and the raw material prepared using the silica being prepared as porous silica material are prepared under part, simple process is former
Material is easy to get and low in cost.Preferably, alkyl silicate is ethyl orthosilicate, and the volume ratio of ethyl orthosilicate and dehydrated alcohol is
1~10: 20~200, preferably 1~5: 20~100.Porous knot is obtained through reduction using minerals such as diatomite in the prior art
The elemental silicon of structure, or porous silica material is obtained using silicon-base alloy pickling, cost of material is high, and wherein the content of silica has
Limit, serious waste of resources are unfavorable for industrialized production.The present invention can controllably synthesize required grain using teos hydrolysis
The silica of diameter size, so that the porous silicon aperture aperture heterogeneous made, is conducive to buffer in charge and discharge process
The volume expansion of silicon.
In some embodiments, the preparation method of above-mentioned negative electrode of lithium ion battery is further comprising the steps of: heating pyrolysis step
Pecvd process in situ is carried out after the completion of rapid, ionized gas is methane or acetylene.PECVD(Plasma Enhanced
Chemical Vapor Deposition) refer to the chemical vapour deposition technique of plasma enhancing.PECVD be by microwave or
Radio frequency etc. makes the gas ionization containing film composed atom, is being partially formed plasma, and plasma chemistry activity is very strong,
It is easy to react, goes out desired film in deposition on substrate.Pecvd process is with heating pyrolytic reaction same in the present invention
One position carries out, no replacement is required position.Ionized gas, such as methane or acetylene are passed through into pyrolysis atmosphere, it can be at low temperature
Carbon is realized in the deposition of porous silicon carbon-carbon composite material surface, further increases carbon material in the coverage degree on porous silica material surface,
Solve the problems, such as that carbon material coats incomplete in porous silicon surface after porous silica material is mixed and is pyrolyzed in a solvent with carbon source, and
Uniform C film is formed on the surface of porous silica material, substantially increases material electric conductivity, while preferably avoiding silicon and electricity
The direct contact for solving liquid, avoids the destruction to material.Pecvd process in situ needs to be passed through inert gas, it is preferable that inert gas
For argon gas and or nitrogen.The total flow of ionized gas and inert gas is 20SCCM~100SCCM, discharge power 150W
~250W, reaction time are 30min~60min.
Embodiment of the present invention also provides a kind of negative electrode of lithium ion battery prepared by the preparation method simultaneously.
Embodiment of the present invention also provides a kind of lithium ion battery simultaneously comprising lithium made from above-mentioned preparation method from
Sub- battery cathode.
Chemical reagent used in the following embodiment is commercially available.
Embodiment 1
The embodiment provides a kind of preparation methods of negative electrode of lithium ion battery, comprising the following steps:
Step 101, synthetic silica: ethyl orthosilicate and dehydrated alcohol are mixed and stirred for according to volume ratio 1: 40
Even, it is 11 that ammonium hydroxide, which is added, and adjusts pH value, stirs 12h, hydrolysis obtains silica.
Step 102, metallothermic reduction: it is with mass ratio by silica and magnesium powder that step 101 is prepared, sodium chloride
1: 1: 15 mixing increases temperature to 650 DEG C with the heating rate of 5 DEG C/min, keeps the temperature cooling after 7h, then under protection of argon gas
The hydrochloric acid that concentration is 1mol/L is added and removes impurity, adds the complete silica of the hydrofluoric acid removal unreacted of 5wt.%, uses
The time of above two acid soak is 12h.Finally washing is dried to obtain porous silica material.
Step 103, preparation battery cathode: the porous silica material and polymethyl methacrylate that step 102 is prepared
It is dispersed in N-Methyl pyrrolidone with the mixing of mass ratio 1: 1, after mechanical mixture stirs 5h, is coated on copper foil, in argon atmospher
It increases temperature in enclosing with the heating rate of 5 DEG C/min to be pyrolyzed to 500 DEG C, pyrolysis time 3h can be prepared by lithium-ion electric
Pond cathode.
Embodiment 2
The embodiment provides a kind of preparation methods of negative electrode of lithium ion battery, comprising the following steps:
Step 101, synthetic silica: ethyl orthosilicate and dehydrated alcohol are mixed and stirred for according to volume ratio 1: 20
Even, it is 8 that ammonium hydroxide, which is added, and adjusts pH value, stirs 12h, hydrolysis obtains silica.
Step 102, metallothermic reduction: it is with mass ratio by silica and magnesium powder that step 101 is prepared, sodium chloride
1: 1.1: 20 mixing increases temperature to 700 DEG C with the heating rate of 5 DEG C/min, keeps the temperature cooling after 12h, so under protection of argon gas
The hydrochloric acid that concentration is 1mol/L is added afterwards and removes impurity, adds the complete titanium dioxide of the hydrofluoric acid removal unreacted of 0.3wt.%
Silicon, the time with above two acid soak are 12h.Finally washing is dried to obtain porous silica material.
Step 103, preparation battery cathode: the porous silica material and polyvinyl alcohol that step 102 is prepared are with mass ratio 1
: 1.2 mixing are dispersed in tetrahydrofuran, after mechanical mixture stirs 5h, are coated on copper foil, with 5 DEG C/min in argon atmosphere
Heating rate increase temperature and be pyrolyzed to 500 DEG C, pyrolysis time 2h can be prepared by negative electrode of lithium ion battery.
Embodiment 3
The embodiment provides a kind of preparation methods of negative electrode of lithium ion battery, comprising the following steps:
Step 101, synthetic silica: ethyl orthosilicate and dehydrated alcohol are mixed and stirred for according to volume ratio 1: 20
Even, it is 10 that ammonium hydroxide, which is added, and adjusts pH value, stirs 10h, hydrolysis obtains silica.
Step 102, metallothermic reduction: it is with mass ratio by silica and magnesium powder that step 101 is prepared, sodium chloride
1: 0.9: 15 mixing increases temperature to 650 DEG C with the heating rate of 5 DEG C/min, keeps the temperature cooling after 6h, so under protection of argon gas
The hydrochloric acid that concentration is 1.5mol/L is added afterwards and removes impurity, adds the complete titanium dioxide of the hydrofluoric acid removal unreacted of 3wt.%
Silicon, the time with above two acid soak are 10h.Finally washing is dried to obtain porous silica material.
Step 103, preparation battery cathode: the porous silica material and Kynoar that step 102 is prepared are with quality
It is dispersed in n,N-Dimethylformamide than 1: 0.8 mixing, after mechanical mixture stirs 5h, is coated on copper foil, in argon atmosphere
In temperature increased with the heating rate of 5 DEG C/min be pyrolyzed to 300 DEG C, pyrolysis time 5h can be prepared by lithium ion battery
Cathode.
Embodiment 4
The embodiment provides a kind of preparation methods of negative electrode of lithium ion battery, comprising the following steps:
Step 101, synthetic silica: ethyl orthosilicate and dehydrated alcohol are mixed and stirred for according to volume ratio 1: 50
Even, it is 8 that ammonium hydroxide, which is added, and adjusts pH value, stirs 12h, hydrolysis obtains silica.
Step 102, metallothermic reduction: it is with mass ratio by silica and magnesium powder that step 101 is prepared, sodium chloride
1: 1: 10 mixing increases temperature to 750 DEG C with the heating rate of 5 DEG C/min, keeps the temperature cooling after 3h, then under protection of argon gas
The hydrochloric acid that concentration is 2mol/L is added and removes impurity, adds the complete silica of the hydrofluoric acid removal unreacted of 5wt.%, uses
The time of above two acid soak is 12h.Finally washing is dried to obtain porous silica material.
Step 103, preparation battery cathode: the porous silica material and hydroxypropyl cellulose that step 102 is prepared are with matter
Amount than 1: 1 mixing be dispersed in dehydrated alcohol, mechanical mixture stir 5h after, be coated on copper foil on, in argon atmosphere with 5 DEG C/
The heating rate of min increases temperature and is pyrolyzed to 600 DEG C, and pyrolysis time 1h can be prepared by negative electrode of lithium ion battery.
Embodiment 5
The embodiment provides a kind of preparation methods of negative electrode of lithium ion battery, comprising the following steps:
Step 101, synthetic silica: ethyl orthosilicate and dehydrated alcohol are mixed and stirred for according to volume ratio 1: 30
Even, it is 10 that ammonium hydroxide, which is added, and adjusts pH value, stirs 12h, hydrolysis obtains silica.
Step 102, metallothermic reduction: it is with mass ratio by silica and magnesium powder that step 101 is prepared, sodium chloride
1: 0.8: 10 mixing increases temperature to 650 DEG C with the heating rate of 5 DEG C/min, keeps the temperature cooling after 4h, so under protection of argon gas
The hydrochloric acid that concentration is 1mol/L is added afterwards and removes impurity, adds the complete silica of the hydrofluoric acid removal unreacted of 5wt.%,
Time with above two acid soak is 12h.Finally washing is dried to obtain porous silica material.
Step 103, preparation battery cathode: the porous silica material and polyacrylonitrile that step 102 is prepared are with mass ratio 1
: 0.5 mixing is dispersed in N-Methyl pyrrolidone, after mechanical mixture stirs 5h, is coated on copper foil, with 5 in argon atmosphere
DEG C/heating rate of min increases temperature and is pyrolyzed to 450 DEG C, pyrolysis time 0.5h is carried out in situ after pyrolysis
Pecvd process, ionized gas are methane, and wherein methane, argon gas total flow are 60SCCM, and methane and argon flow ratio are 1: 2,
Discharge power is 200W, and discharge time 30min can be prepared by negative electrode of lithium ion battery.
Referring to the X-ray diffraction spectrum figure of Fig. 2 porous silica material, silica obtains pure phase after metallothermic reduction
Silicon；Referring to the graph of pore diameter distribution of Fig. 3 porous silica material, pore-size distribution is 2nm~150nm, wherein there is a Qiang Feng at 3nm.
The partial size of porous silica material is 180nm, specific surface area 124m in the present embodiment2/g.Above-mentioned porous silica material is mixed with carbon source
After coating and being pyrolyzed, silicon particle is evenly distributed on collector, referring to Fig. 4.The battery that the embodiment of the present invention is prepared
Cathode is used for CR2430 model button cell, and button cell lithium piece specification is ф 18*0.5mm, and pole piece diameter is ф 14mm, voltage
Window is 0.01V~1.5V, current density is that 200mA/g is tested, referring to the cycle performance curve of Fig. 5.The present embodiment
Negative electrode of lithium ion battery first discharge specific capacity is 1756mAh/g, charge specific capacity 1226mAh/g, for the first time coulombic efficiency
69.8%, second of coulombic efficiency is up to 96.7%, and coulombic efficiency is maintained at 99% since the 4th time.Specific capacity after 40 circulations
It is maintained at 1000mAh/g or so, capacity retention ratio 81%.The resistivity of negative electrode of lithium ion battery is 0.933Ohm*cm, conductance
Rate is 1.071S/cm.
The above description is merely a specific embodiment, but simultaneously difference is limited to this to protection scope of the present invention, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (18)
1. a kind of preparation method of negative electrode of lithium ion battery, which comprises the following steps: by porous silica material and carbon source
Be scattered in solvent and mix, be then coated on collector, and in atmosphere of inert gases heating pyrolysis to get arriving lithium-ion electric
Pond cathode.
2. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the porous silica material
Partial size is 50nm~500nm, and aperture is 1nm~200nm, specific surface area 100m2/ g~280m2/g。
3. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the porous silica material with
The mass ratio of the carbon source is 1: 0.01~1.2, and preferred mass ratio is 1: 0.5~1.2.
4. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the carbon source be selected from by
Polyacrylonitrile, Kynoar, polyvinyl alcohol, polyethylene glycol, guar gum, polymethyl methacrylate, hydroxypropyl cellulose and
Polyethylene glycol oxide group is at least one of in groups.
5. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the solvent be selected from by
N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, deionized water, dehydrated alcohol, tetrahydrofuran, N-Methyl pyrrolidone and
Dimethyl sulfoxide group is at least one of in groups.
6. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the temperature of the pyrolysis is
300 DEG C~1000 DEG C, time of pyrolysis is 0.5h~12h, preferably 300 DEG C~800 DEG C of pyrolysis temperature, pyrolysis time 0.5h~
5h, 300 DEG C~600 DEG C of more preferable pyrolysis temperature, pyrolysis time 0.5h~3h.
7. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the collector is copper
Foil, nickel foil, carbon cloth, stainless (steel) wire or titanium foil.
8. the preparation method of negative electrode of lithium ion battery according to claim 1, which is characterized in that the porous silica material
Preparation method the following steps are included:
Silica is mixed with metallic reducing agent, fused salt, under inert gas protection, temperature reaction, reaction is completed and cooling
Use acid soak afterwards to get the porous silica material is arrived.
9. the preparation method of negative electrode of lithium ion battery according to claim 8, which is characterized in that the silica, gold
Belong to reducing agent, the mass ratio of fused salt is 1: 0.1~5: 1~30, preferably 1: 0.2~2: 5~20.
10. according to right want 8 described in negative electrode of lithium ion battery preparation method, which is characterized in that the porous silica material
Reaction temperature is 200 DEG C~1000 DEG C in preparation process, and the reaction time is 0.5h~12h；Preferable reaction temperature 650 DEG C~750
DEG C, reaction time 1h~7h.
11. the preparation method of negative electrode of lithium ion battery according to claim 8, which is characterized in that the behaviour of the acid soak
Make specifically: first be added concentration be 0.1mol/L~5mol/L hydrochloric acid or sulfuric acid remove impurity, add 0.3wt.%~
The complete silica of the hydrofluoric acid removal unreacted of 5wt.%.
12. the preparation method of negative electrode of lithium ion battery according to claim 8, which is characterized in that the metallic reducing agent
By selected from by lithium, sodium, potassium, magnesium and aluminium group at least one of in groups.
13. the preparation method of negative electrode of lithium ion battery according to claim 8, which is characterized in that the fused salt is selected from gold
Belong to halide, preferably sodium chloride and/or potassium chloride.
14. the preparation method of negative electrode of lithium ion battery according to claim 8, which is characterized in that the silica
Preparation method the following steps are included:
After alkyl silicate is mixed with dehydrated alcohol, ammonium hydroxide is added, adjusting pH value is 8~11, and reaction obtains silica.
15. the preparation method of negative electrode of lithium ion battery according to claim 14, which is characterized in that the alkyl silicate
For ethyl orthosilicate, the volume ratio of the ethyl orthosilicate and the dehydrated alcohol is 1~10: 20~200, preferably 1~5:
20~100.
16. according to claim 1 to the preparation method of negative electrode of lithium ion battery described in any one of 15, which is characterized in that also
The following steps are included: carrying out pecvd process in situ after the completion of heating pyrolysis step, ionized gas is methane or acetylene.
17. a kind of negative electrode of lithium ion battery that the preparation method as described in any one of claims 1 to 16 is prepared.
18. a kind of lithium ion battery, which is characterized in that including the preparation method system as described in any one of claims 1 to 16
Standby obtained negative electrode of lithium ion battery.
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| CN110165143A (en) * | 2019-05-24 | 2019-08-23 | 东莞市安德丰电池有限公司 | A kind of lithium battery electrode plate and the preparation method and application thereof |
| CN111446432A (en) * | 2020-04-20 | 2020-07-24 | 上海交通大学 | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery |
| CN111477835A (en) * | 2020-04-26 | 2020-07-31 | 四川聚创石墨烯科技有限公司 | Method for continuously preparing current collector-silicon-carbon negative electrode |
| CN113666354A (en) * | 2020-05-13 | 2021-11-19 | 北京小米移动软件有限公司 | Preparation method of silicon-carbon composite material, silicon negative electrode piece and battery |
| CN113875041A (en) * | 2019-05-30 | 2021-12-31 | 新强能电池公司 | Direct coating of electrodes in silicon-dominated anode cells |
| CN114551886A (en) * | 2022-02-23 | 2022-05-27 | 湖北亿纬动力有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
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