CN108923035A - A kind of preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material - Google Patents

A kind of preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material Download PDF

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CN108923035A
CN108923035A CN201810778934.6A CN201810778934A CN108923035A CN 108923035 A CN108923035 A CN 108923035A CN 201810778934 A CN201810778934 A CN 201810778934A CN 108923035 A CN108923035 A CN 108923035A
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lithium ion
nano
ion battery
negative pole
carbon composite
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CN108923035B (en
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陈建
刘平
李琳
龚勇
周孝林
辜其隆
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Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of lithium ion battery preparation methods of nano-silicone wire/carbon composite negative pole material, include the following steps：Fiber filament is made in internal layer presoma emulsion and outer layer presoma emulsion by using coaxial electrostatic spinning technology, then carbonization treatment obtains nano-silicone wire/carbon composite negative pole material by load freeze-drying-load hot pressing-load heat treatment process and twice.Lithium ion battery of the invention nano-silicone wire/carbon anode material, fibre diameter is small and even thickness, large specific surface area, carbon layers having thicknesses are reduced by load heat treatment, with good specific capacity and cycle performance, the diffusive migration path of lithium ion is effectively shortened, avoiding silicon nanoparticle leads to material dusting because of Volumetric expansion, the problems such as structure collapses, makes the present invention have a good application prospect.

Description

A kind of preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery nano-silicone wire/carbon composite negative pole The preparation method of material.
Background technique
Lithium ion battery has big capacity, high working voltage, service life cycle length, nuclear power holding capacity strong, allows work Outstanding advantages of making wide temperature range, environmentally protective and memory-less effect, has been widely used in electronic product now, It is expected that touch will be up to 1,193,100,000,000 dollars for the year two thousand twenty market rule.Therefore, lithium ion battery applications are in energy stores and electric car It has broad prospects.
But the internal driving of lithium ion battery is higher at present, operating voltage changes greatly, at high cost, it is necessary to have spy Different protection circuit and the power density for pure electric automobile and capacity all need to be further increased.In addition, restricting lithium The key factor of ion battery development is the preparation of battery material, and in existing lithium ion battery material, carbon material is most often The negative electrode material seen.In the long run, since theoretical capacity is high, (up to 4200m Ah/g is current commercialization to silicon based anode material Ten times or more of graphite cathode), the advantages that discharge potential is low, rich reserves, it is considered to be substitute the next-generation lithium ion of graphite One of cell negative electrode material.But silicon during lithium ion is embedding de- along with serious Volumetric expansion (>300%) draw Active material dusting is played, and then loses and contacts with collector and conductive agent, leads to the reduction of battery coulombic efficiency, cycle performance becomes Difference, capacity are decayed rapidly, and the commercialization process of silica-base material is greatly limited.Although nanosizing can be effectively relieved Lithium ion diffusion path is shortened in volume expansion, improves material electrochemical activity, reduces electrochemical reaction polarization；But partial size is got over Small easier reunion, specific surface area is bigger, is less susceptible to prepare.
Lead to material dusting because of volume expansion in charge and discharge process to alleviate silicon, structure collapses are de- with electrode slice From, and then the problems such as cause electrode conductivuty to be deteriorated, (Journal of Power Sources, 2010,195 (15) such as Wang:
The compound influence for comparing material electrochemical performance of silicon-carbon 5052-5056) is had studied using electrostatic spinning technique, works as silicon Carbon mass ratio is 23:Nanofiber has optimal chemical property when 77, and reversible specific capacity is up to 1240mAh/g；But The high rate performance and cycle performance of material are bad.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of lithium ion battery nano-silicons The preparation method of carbon compound cathode materials solves diffusive migration path length of the existing lithium ion battery in charge and discharge process, receives Rice silicon particle leads to material dusting because of Volumetric expansion, and structure collapses are detached from electrode slice, and then cause electrode conductivuty The problems such as variation.
To achieve the above object, the present invention adopts the following technical scheme that：A kind of lithium ion battery nano-silicone wire/carbon Compound Negative The preparation method of pole material, includes the following steps：
1) after being impregnated with nano silica fume with suitable coupling agent, polymer A is added and spin solvent, object A to be polymerized are completely molten Internal layer presoma emulsion is made in 1~5h of ultrasonic disperse after solution；Fibre-forming polymer B is dissolved in spin solvent, outer layer is made Presoma emulsion；Internal layer presoma emulsion and outer layer presoma emulsion are made up coaxially of coaxial electrostatic spinning technology Fiber filament, by the coaxial fiber filament heating except solvent obtains cladding presoma；
2) it is obtained after the cladding presoma that step 1) obtains being carried out load freeze-drying, load hot pressing and load heat treatment Nano-silicon/polymer A/ polymer B composite fibre；
3) nano-silicon/polymer A/ polymer B composite fibre for preparing step 2) carries out under inert gas protection After carbonization treatment, grinds and be sieved with 300~400 mesh of porous sieve, obtain lithium ion battery nano-silicone wire/carbon composite negative pole material.
Further, the spin solvent is water, n,N-Dimethylformamide, acetone, carbon trichloride, N, N- dimethyl second Amide or tetrahydrofuran etc., the coupling agent are Y- aminopropyl triethoxysilane, cetyl trimethylammonium bromide, second two Alcohol, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane (KH-560) or polyvinylpyrrolidone etc..
Further, the fibre-forming polymer A and fibre-forming polymer B is respectively PVDF (Kynoar), TPU (poly- ammonia Ester), PI (polyimides), PVP (polyvinylpyrrolidone), PMMA (polymethyl methacrylate), PVA (polyvinyl alcohol) or PAN (polyacrylonitrile) etc..
Further, the mass ratio of the nano silica fume and fibre-forming polymer A are 1:20~1:4.
Further, the concentration of polymer B is 8~15% in the outer layer presoma emulsion；The internal layer presoma cream The concentration of polymer A is 8~15% in turbid.
Further, the load freeze-drying refers to 10~12h of processing in -80~-50 DEG C of vacuum freezing drying oven, Load capacity is 50~500g.
In this way, can effectively prevent fiber because causing fiber to become by thermally-induced water loss by load freeze drying process Shape, structure collapses.
Further, temperature is 100~150 DEG C in load heat treatment, and the time is 0.5~2h, load capacity is 50~ 500g。
In this way, it is multiple to prepare the nanometer that average diameter is 100~160nm by control different loads and heat treatment temperature technique Condensating fiber；More evenly thinner nanofibers can be obtained compared with prior art, reduce carbon layers having thicknesses, effectively shorten lithium The diffusion mobility path of ion.
Further, hot pressing temperature is 130~140 DEG C in the load hot pressing, and hot pressing time is 0.5~1h, and load capacity is 0.5~4kg.
In this way, can effectively prevent fiber filament because electrostatic crimps by load hot-pressing processing, be carbonized temperature distortion, and fiber is molten Melt.
Further, the carbonization treatment is divided to two stages an of carbonization treatment and secondary carbonization treatment, the primary carbonization Processing is after being warming up to 200~500 DEG C of 1~12h of sintering with 2~5K/min, then is warming up to 600~800 DEG C of burnings with 1~3K/min 1~12h of knot, is cooled to room temperature；The secondary carbonization treatment is that 700~900 DEG C of 1~12h of sintering are warming up to 4~6K/min, It is cooled to room temperature.
In this way, carbon layers having thicknesses can be controlled according to actual needs, shorten lithium ion diffusive migration path.In addition, by double carbon The nano-silicon of layer cladding can more effectively alleviate the Volumetric expansion of silicon nanoparticle, while also improve the conductance of material Rate.
Compared with prior art, the present invention has the advantages that：
1, the present invention is in preparing lithium ion battery nano-silicone wire/carbon composite negative pole material, the coaxial electrostatic spinning skill of use Art can prepare uniform, stable, continuous elongated fiber filament by controlling spinning parameter, and filametntary average diameter is Between 300~600nm；It, can be by controlling different loads using load freeze-drying-load hot pressing-load heat treatment process More evenly thinner nanofibers are prepared with treatment temperature technique, average diameter, also can be effective between 100~160nm Prevent fiber filament because dehydration or it is heated due to deform, crimped because of electrostatic interaction, eventually lead to structure collapses；At secondary carbonization Science and engineering skill forms carbon coating layer on nanofibers surface, can control carbon layers having thicknesses according to demand, the lithium ion that effectively shortens expands Migration path is dissipated, double carbon-coatings can more effectively alleviate the Volumetric expansion of silicon nanoparticle, also substantially increase silicon carbon material Specific surface area, improve the electro-chemical activity of material.
2, lithium ion battery prepared by the present invention is small and uniform with nano-silicone wire/carbon composite negative pole material partial size, specific surface area Greatly, therefore there is good specific capacity and cycle performance, silicon nanoparticle, which has been effectively relieved, because of Volumetric expansion leads to material Feed powder, structure collapses are detached from electrode slice, and then the problems such as cause electrode conductivuty to be deteriorated, and have the present invention good Application prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of self-made clamp；
Fig. 2 is the XRD spectra of nano-silicone wire/carbon composite negative pole material made from embodiment 1；
Fig. 3 is the SEM figure of the cladding forerunner's composite material obtained of embodiment 1；
Fig. 4 is the SEM figure of nano-silicone wire/carbon composite negative pole material made from embodiment 1；
Fig. 5 is ratio of the button cell at 100mA/g that nano-silicone wire/carbon composite negative pole material made from embodiment 1 is cathode Capacity and cycle-index figure.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.Not to experiment in following embodiment What method was illustrated, be routine operation, and agents useful for same is common commercially available.
One, the preparation method of a kind of lithium ion battery nano-silicone wire/carbon composite negative pole material
Embodiment 1
1) precise 2.8g polyacrylonitrile (PAN) powder, 14.4g n,N-Dimethylformamide (DMF) are small in 50ml In beaker, and it is placed in constant temperature in 50 DEG C of oil bath pans and stirs 3h, and the ultrasonic disperse 4h after PAN powder is completely dissolved, obtaining concentration is 14% outer layer presoma emulsion, for use；
2) precise 0.4g nano silica fume (30nm) and 0.03g Y- aminopropyl triethoxysilane (KH550) in 5min is infiltrated in 50ml small beaker, adds 2.6g polymethyl methacrylate (PMMA) powder, 17.4g N, N- dimethyl methyl After amide (DMF), places it in constant temperature in 35 DEG C of oil bath pans and stir 3h, after PMMA powder is completely dissolved, ultrasonic 2h obtains concentration For 13% internal layer presoma emulsion, for use；
3) it selects the syringe of two 20ml to draw internal layer emulsion and outer layer emulsion respectively, and is separately fixed at It injects on flow speed controller, and the related spinning parameter of opening electrospinning device adjusting (40 DEG C of spinning temperature, humidity 36%, syringe needle Diameter (outer 2.5mm, interior 1.8mm), spinning voltage 22.1KV, revolving speed 200r/min, flow velocity 1.213ul/min) it is made coaxial fine Silk is tieed up, for use；
4) coaxial fiber filament made from step 3) is put into 60 DEG C of air dry oven to take out after removing solvent 30min and is obtained Forerunner's composite material is coated, cuts and grows up 10.0cm (± 0.2cm), the thin slice of wide 5.0cm (± 0.2cm), for use；
5) use self-made clamp (such as Fig. 1), gripping step 4) made from thin slice, be placed in -70 DEG C of vacuum freezing drying oven and apply Add load capacity 300g, after being freeze-dried 10h, then at load capacity 2kg, 130 DEG C of hot pressing 30min；Finally in 140 DEG C of forced air drying Apply load capacity 300g in case, processing 60min obtains nano-silicon/polymer A/ polymer B composite fibre.
6) it is put into togerther after nano-silicon/polymer A/ polymer B composite fibre made from self-control iron plate pressing step 5) In quartz boat, it is placed in tube furnace, under protection of argon gas, after being warming up to 280 DEG C of heat preservation 2h with 2K/min, with 1K/min in liter Temperature is to 780 DEG C of heat preservation 1h, after being cooled to room temperature；It is warming up at 800 DEG C with 5K/min again and keeps the temperature the secondary carbonization treatment of 2h progress, it is cold But to after room temperature, finally the product after carbonization is placed in agate mortar and is ground, porous sieve (400 mesh) is sieved to obtain Si/ CPMMA-CPANNano-silicone wire/carbon composite negative pole material.
Embodiment 2
1) precise 2.8g polyacrylonitrile (PAN) powder, 14.4g n,N-Dimethylformamide (DMF) are small in 50ml In beaker, and it is placed in 50 DEG C of oil bath pans constant temperature and stirs 3h, and ultrasonic disperse 4h obtains concentration and is after PAN powder is completely dissolved 14% outer layer presoma emulsion, for use；
2) precise 0.4g nano silica fume (30nm) and 0.03g Y- aminopropyl triethoxysilane (KH550) in 5min is infiltrated in 50ml small beaker, adds 2.8g polyacrylonitrile (PAN) powder, 14.4g n,N-Dimethylformamide (DMF) Afterwards, place it in 50 DEG C of oil bath pans constant temperature and stir 3h, after PAN powder is completely dissolved, ultrasonic 2h, obtain concentration be 14% it is interior Layer presoma emulsion, for use；
3) it selects the syringe of two 20ml to draw internal layer emulsion and outer layer emulsion respectively, and is separately fixed at It injects on flow speed controller, and the related spinning parameter of opening electrospinning device adjusting (40 DEG C of spinning temperature, humidity 36%, syringe needle Diameter (outer 2.5mm, interior 1.8mm), spinning voltage 23.0KV, revolving speed 200r/min, flow velocity 1.213ul/min) it is made coaxial fine Silk is tieed up, for use；
4) coaxial fiber filament made from step 3) is put into 60 DEG C of air dry oven to take out after removing solvent 30min and is obtained Forerunner's composite material is coated, cuts and grows up 10.0cm (± 0.2cm), the thin slice of wide 5.0cm (± 0.2cm), for use；
5) use self-made clamp (such as Fig. 1), gripping step 4) made from thin slice, be placed in -80 DEG C of vacuum freezing drying oven and apply Add load capacity 500g, after being freeze-dried 10h, then at load capacity 4kg, 130 DEG C of hot pressing 30min；Finally in 150 DEG C of forced air drying Apply load capacity 500g in case, processing 60min obtains nano-silicon/polymer A/ polymer B composite fibre.
6) it is put into togerther after nano-silicon/polymer A/ polymer B composite fibre made from self-control iron plate pressing step 5) In quartz boat, it is placed in tube furnace, under protection of argon gas, after being warming up to 280 DEG C of heat preservation 2h with 5K/min, with 1K/min in liter Temperature is to 780 DEG C of heat preservation 1h, after being cooled to room temperature；It is warming up at 800 DEG C with 5K/min again and keeps the temperature the secondary carbonization treatment of 2h progress, it is cold But to after room temperature, finally the product after carbonization is placed in agate mortar and is ground, porous sieve (400 mesh) is sieved to obtain Si/ CPAN-CPANNano-silicone wire/carbon composite negative pole material.
Embodiment 3
1) precise 2.8g Kynoar (PVDF) powder, 14.4g n,N-Dimethylformamide (DMF) is in 50ml In small beaker, and it is placed in constant temperature in 35 DEG C of oil bath pans and stirs 3h, and ultrasonic disperse 4h obtains concentration after PVDF powder is completely dissolved For 14% outer layer presoma emulsion, for use；
2) precise 0.4g nano silica fume (30nm) and 0.03gY- aminopropyl triethoxysilane (KH550) are in 50 ml 5min is infiltrated in small beaker, adds 2.6g polymethyl methacrylate (PMMA) powder, 17.4g n,N-Dimethylformamide (DMF) it after, places it in constant temperature in 35 DEG C of oil bath pans and stirs 3h, after PMMA powder is completely dissolved, ultrasonic 2h, obtaining concentration is 12% internal layer presoma emulsion, for use；
3) it selects the syringe of two 20ml to draw internal layer emulsion and outer layer emulsion respectively, and is separately fixed at It injects on flow speed controller, and the related spinning parameter of opening electrospinning device adjusting (40 DEG C of spinning temperature, humidity 36%, syringe needle Diameter (outer 2.5mm, interior 1.8mm), spinning voltage 20.0KV, revolving speed 200r/min, flow velocity 1.213ul/min) fiber is made Silk, for use；
4) fiber filament made from step 3) is put into 60 DEG C of air dry oven to take out after removing solvent 30min and is coated Forerunner's composite material cuts and grows up 10.0cm (± 0.2cm), the thin slice of wide 5.0cm (± 0.2cm), for use；
5) use self-made clamp (such as Fig. 1), gripping step 4) made from thin slice, be placed in -70 DEG C of vacuum freezing drying oven and apply Add load capacity 300g, after being freeze-dried 10h, then at load capacity 2kg, 130 DEG C of hot pressing 30min；Finally in 140 DEG C of forced air drying Apply load capacity 300g in case, processing 60min obtains nano-silicon/polymer A/ polymer B composite fibre.
6) it is put into togerther after nano-silicon/polymer A/ polymer B composite fibre made from self-control iron plate pressing step 5) In quartz boat, it is placed in tube furnace, under protection of argon gas, after being warming up to 300 DEG C of heat preservation 2h with 5K/min, with 1K/min in liter Temperature is to 800 DEG C of heat preservation 1h, after being cooled to room temperature；It is warming up at 800 DEG C with 5K/min again and keeps the temperature the secondary carbonization treatment of 2h progress, it is cold But to after room temperature, finally the product after carbonization is placed in agate mortar and is ground, porous sieve (400 mesh) is sieved to obtain Si/ CPMMA-CPVDFNano-silicone wire/carbon composite negative pole material.
Two, performance verification
1, using the structure of X-ray diffraction analysis instrument analysis 1 gained nano-silicone wire/carbon anode material of embodiment, such as Fig. 2 It is shown.
As seen from Figure 2, Si/C prepared by embodiment 1 provided by the inventionPMMA-CPANNano-silicone wire/carbon composite negative pole There are a sharp diffraction maximum, (111) crystal faces of corresponding silicon, at 2 θ=47 ° and 2 θ=56 ° at 2 θ=28.5 ° for material There are two strong peaks, (220) and (311) crystal face of corresponding silicon illustrates to introduce in composite material after pure silicon carbonization to pure silicon Crystal structure and crystal form do not influence to still fall within cubic system, carbon coating and the structure useless for influencing negative electrode material；Relative to pure The intensity that nano-silicone wire/carbon composite material corresponds to peak for silicon is reduced, and other impurity peaks does not occur and occurs, illustrates this hair The Si of pure phase has been prepared in the preparation method of bright offer0.1/CPMMA-CPANNano-silicone wire/carbon composite negative pole material.
2, using cladding forerunner's composite material and nano-silicone wire/carbon composite negative pole material obtained by scanning electron microscopic observation embodiment 1 Pattern, as shown in Figure 3 and Figure 4.
From figure 3, it can be seen that the fiber surface of cladding forerunner's composite material is smooth, crosses one another and stack, there is portion on surface Divide reunion silicon powder, a no beading occur, and distribution of SMD is about 300-600nm.
From fig. 4, it can be seen that the fiber surface of nano-silicone wire/carbon composite negative pole material is smooth, crosses one another and stack, surface has There is not phenomenon of rupture in part reunion silicon powder, most of filament contraction, by being carbonized after a series of heat treatment process, fiber Average diameter is less than 160nm, relative to cladding presoma composite fiber diameter, reduces 4 times, largely reduces Carbon layers having thicknesses.
3, the Si/C for preparing embodiment 1PMMA-CPANNano-silicone wire/carbon anode material, acetylene black and aqueous binders, In mass ratio 8:1:1 carries out ingredient, is placed in the slurry of grinding preparation modest viscosity in mortar, is uniformly coated on copper foil and makes Electrode slice is obtained, then electrode slice is assembled into CR2032 button cell in glove box, tests its chemical property.
The CR2032 button cell that will be assembled into carries out 20 cycle performance tests, knot under the current density of 100mA/g Fruit is as shown in Figure 5.
From fig. 5, it can be seen that the Si/C after 20 circulationsPMMA-CPANNano-silicone wire/carbon anode material, except following for the first time Ring attenuation ratio is more serious outer, remaining cyclic specific capacity capacity is more stable, is maintained at 1057mAh/g or so；It is primarily due to double carbon-coatings Structure provides enough spaces for nano silica fume, alleviates volume expansion.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (10)

1. a kind of lithium ion battery preparation method of nano-silicone wire/carbon composite negative pole material, which is characterized in that include the following steps：
1）It is impregnated with nano silica fume with coupling agent, polymer A is added and spin solvent, object A to be polymerized are completely dissolved rear ultrasonic disperse 1 Internal layer presoma emulsion is made in ~ 5h；Polymer B is dissolved in spin solvent, outer layer presoma emulsion is made；Pass through Coaxial fiber filament is made in internal layer presoma emulsion and outer layer presoma emulsion by coaxial electrostatic spinning technology, then will be described same The heating of axis fiber filament obtains cladding presoma except solvent；
2）By step 1）Obtained cladding presoma obtains nanometer after carrying out load freeze-drying, load hot pressing and load heat treatment Silicon/polymer A/ polymer B composite fibre；
3）By step 2）The nano-silicon of preparation/polymer A/ polymer B composite fibre is carbonized under inert gas protection After processing, grinds and be sieved with 300 ~ 400 mesh of porous sieve, obtain lithium ion battery nano-silicone wire/carbon composite negative pole material.
2. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that The spin solvent is water, n,N-Dimethylformamide, acetone, carbon trichloride, n,N-dimethylacetamide or tetrahydrofuran, institute Stating coupling agent is Y- aminopropyl triethoxysilane, cetyl trimethylammonium bromide, ethylene glycol, γ-（2,3- epoxy third Oxygen）Propyl trimethoxy silicane or polyvinylpyrrolidone.
3. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that The polymer A is Kynoar, polyurethane, polyimides, polyvinylpyrrolidone, polymethyl methacrylate, poly- second Enol or polyacrylonitrile；Polymer B is Kynoar, polyurethane, polyimides, polyvinylpyrrolidone, polymethyl Sour methyl esters, polyvinyl alcohol or polyacrylonitrile.
4. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that The mass ratio of the nano silica fume and polymer A are 1:20~1:4.
5. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that The concentration of fibrous polymer A is 8% ~ 15% in the internal layer presoma emulsion, fibrous polymer B in the outer layer presoma emulsion Concentration be 8% ~ 15%.
6. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that The load freeze-drying refers to 10 ~ 12h of processing in -80 ~ -50 DEG C of vacuum freezing drying oven, and load capacity is 50 ~ 500g.
7. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that Temperature is 100 ~ 150 DEG C in the load heat treatment, and the time is 0.5 ~ 2h, and load capacity is 50 ~ 500g.
8. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that Temperature is 130 ~ 140 DEG C in the load hot pressing, and the time is 0.5 ~ 1h, and load capacity is 0.5 ~ 4kg.
9. the preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material according to claim 1, which is characterized in that The carbonization treatment is divided to two stages an of carbonization treatment and secondary carbonization treatment, and a carbonization treatment is with 2 ~ 5 K/ After min is warming up to 200 ~ 500 DEG C of 1 ~ 12h of sintering, then 600 ~ 800 DEG C of 1 ~ 12h of sintering are warming up to 1 ~ 3K/min, are cooled to room Temperature；The secondary carbonization treatment is that 700 ~ 900 DEG C of 1 ~ 12h of sintering are warming up to 4 ~ 6 K/min, is cooled to room temperature.
10. a kind of lithium ion battery, including negative electrode material, which is characterized in that the negative electrode material is any using claim 1 ~ 9 Lithium ion battery described in is prepared with nano-silicone wire/carbon composite negative pole material preparation method.
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CN110112405A (en) * 2019-05-29 2019-08-09 哈尔滨理工大学 A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof
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CN112271297A (en) * 2020-10-20 2021-01-26 西安工程大学 Grid type laminated structure material synthesis and molding integrated silicon cathode and preparation method thereof
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CN113493943A (en) * 2020-03-18 2021-10-12 中国科学院山西煤炭化学研究所 Si/C composite fiber material and preparation method and application thereof
CN113493944A (en) * 2020-03-18 2021-10-12 中国科学院山西煤炭化学研究所 Spinning solution and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN109802139A (en) * 2018-12-29 2019-05-24 成都市银隆新能源有限公司 The preparation method and battery of a kind of aqueous binders, battery
CN109802139B (en) * 2018-12-29 2022-05-06 成都市银隆新能源有限公司 Preparation method of battery and battery
CN109888215A (en) * 2019-02-19 2019-06-14 福建翔丰华新能源材料有限公司 A method of nucleocapsid structure lithium ion battery negative electrode material is prepared with electrostatic spinning
CN110212170B (en) * 2019-05-06 2020-12-04 上海颐行高分子材料有限公司 Silicon-based negative electrode material prepared by solid-phase hot pressing and preparation method thereof
CN110212170A (en) * 2019-05-06 2019-09-06 上海颐行高分子材料有限公司 A kind of standby obtained silicon based anode material and preparation method thereof of solid phase hot pressing
CN110112405B (en) * 2019-05-29 2021-05-18 哈尔滨理工大学 Core-shell structure silicon/carbon fiber flexible composite electrode material and preparation method and application thereof
CN110112405A (en) * 2019-05-29 2019-08-09 哈尔滨理工大学 A kind of core-shell structure silicon/carbon fiber flexible combination electrode material and the preparation method and application thereof
CN112531144A (en) * 2019-09-17 2021-03-19 通用汽车环球科技运作有限责任公司 Method of preparing silicon-based electrode comprising natural carbonaceous filament and battery cell using the same
CN113493943A (en) * 2020-03-18 2021-10-12 中国科学院山西煤炭化学研究所 Si/C composite fiber material and preparation method and application thereof
CN113493944A (en) * 2020-03-18 2021-10-12 中国科学院山西煤炭化学研究所 Spinning solution and preparation method thereof
CN113493944B (en) * 2020-03-18 2022-09-23 中国科学院山西煤炭化学研究所 Spinning solution and preparation method thereof
CN112271297A (en) * 2020-10-20 2021-01-26 西安工程大学 Grid type laminated structure material synthesis and molding integrated silicon cathode and preparation method thereof
CN112271297B (en) * 2020-10-20 2022-09-06 西安工程大学 Grid type laminated structure material synthesis and molding integrated silicon cathode and preparation method thereof
CN113422009A (en) * 2021-06-01 2021-09-21 广东工业大学 Lithium ion battery cathode material and preparation method and application thereof
CN113422009B (en) * 2021-06-01 2022-03-18 广东工业大学 Lithium ion battery cathode material and preparation method and application thereof
CN114639807A (en) * 2022-03-04 2022-06-17 东华大学 Porous silicon nanoparticle/porous carbon nanofiber composite electrode material and preparation method and application thereof

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