CN108448090A - A kind of preparation method of lithium battery silicon-carbon composite material - Google Patents
A kind of preparation method of lithium battery silicon-carbon composite material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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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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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
A kind of preparation method of lithium battery silicon-carbon composite material, the present invention relates to the preparation methods of lithium battery silicon carbon anode material, it will solve the technical problem of the stability difference of existing silicon-carbon nucleocapsid lithium cell cathode material.The method of the present invention：One, silicon powder is heat-treated；Two, it silicon powder crushing grinding and sieves；Three, it is coated with resin；Four, high temperature carbonization is handled；Five, remaining SiO is removed with hydrofluoric acid2.The discharge capacity for the first time of the silicon-carbon composite cathode material of the present invention is 800~1142mAh/g, coulombic efficiency is up to 82%~91% for the first time, and coulombic efficiency is suitable with coulombic efficiency for the first time after 100 cycles, it still can reach 84%~92%, it is easy to operate, raw material is easy to get, and is easy to mass produce, and can be used for electrochemical energy field of material technology.
Description
Technical field
The present invention relates to the preparation methods of lithium battery silicon carbon anode material.
Background technology
Requirement with electronic device to battery performance is higher and higher and the enhancing of people's environmental consciousness, and there is an urgent need to height
Energy, environmental-friendly green power supply, traditional secondary cell such as nickel-cadmium cell are difficult to meet growing requirement.Due to lithium
Minimum (- 3.04V is relative to standard hydrogen electrode), the primary battery being made of lithium with quality minimum (M=6.941), electrode potential
Have the characteristics that open-circuit voltage is high, energy density is very big, therefore lithium battery is used widely.Since being commercialized since 1991,
Lithium ion battery is always maintained at quick development, leading role is occupied in the markets such as mobile phone, laptop, video camera
Position, instead of traditional cadmium-nickel accumulator and metal-hydrogen nickel battery, becomes the main power source of Small Civil electronic product.
Commercial Li-ion battery negative material generally uses graphite type material at present, but the theoretical lithium storage content of graphite
Only 372mAh/g is susceptible to analysis lithium phenomenon in high current charge-discharge, cannot meet high performance lithium ion battery development
Demand, therefore it is extremely urgent to develop novel high-performance negative material.
Silicon has the embedding lithium capacity (about 4200mAh/g) of theory of superelevation, is ten times or more of present commercial graphite cathode,
The electric discharge of silicon only has about 0.2V to lithium current potential, less than most alloy types and metal oxide-type negative material.Low work electricity
Pressure and high quality specific capacity so that there is silicon-based anode very high energy density to be accordingly regarded as the lithium ion for most having development potentiality
Negative electrode battery material.But during removal lithium embedded, silicon will produce serious volume change (>300%), and then lead to material powder
Change, loses electrical contact with collector and conductive agent, capacity is caused to decay rapidly.The unstable solid electrolyte interface film of silicon face
(SEI films) also seriously limits its cycle life.During removal lithium embedded, with the expansion and contraction of silicon, the SEI of silicon face
Film is constantly deformed, is ruptured, and the silicon face exposed can form new SEI films again, and leading to SEI films, gradually accumulation thickens, and greatly hinders
Hinder diffusion of the lithium ion to silicon particle, reduces the embedding lithium capacity of active material.In addition, the electronic conductivity of silicon is very low (about
It is 10-3Scm-1), very slowly (lithium ion diffusion coefficient is 10 for the lithium ion diffusion in silicium cathode-14cm2s-1To 10-13cm2s-1
Between).Although silicon substrate lithium cell cathode material has vast potential for future development, huge cubical expansivity and low electronics are led
Electric rate seriously limits silicium cathode and plays theoretical capacity, and causes its high rate performance very poor.
The drawbacks of how solving silicon based anode material becomes the most important thing in lithium cell cathode material field.Nearly ten years
Scientific worker has carried out a large amount of exploratory development, and a kind of method is to prepare the silicon materials of nanoscale, such as nanosphere, silicon nanometer
Pipe, silicon nanowires etc., the absolute volume by reducing silicon change to alleviate its bulk effect, another method is to silicon materials
It is middle to introduce the second phase with very good mechanical properties and electric conductivity, various silicon based composite materials are prepared, such as silicon/carbon compound cathode
Material, silicon-base alloy etc. inhibit the bulk effect of silicon by the second mutually excellent mechanical performance, and highly conductor phase also can
The overall conductivity for increasing composite material, is conducive to the raising of high rate performance.
In above-mentioned silicon based composite material especially based on the compound nucleocapsid of silicon-carbon.The compound nucleocapsid of silicon-carbon is a kind of
Very promising negative material, this also results in more and more concerns in several years.Since 1996, there is researcher pass successively
Note micron or the silicon particle of nanostructure are combined with carbon phase.The main reason for it attracts attention is this compound to take full advantage of two
The property of kind material：The embedding lithium capacity of height and carbon of silicon excellent mechanical performance and electric conductivity, the mechanical elasticity of carbon material can
The huge volume expansion of silicon is buffered, while high electronic conductivity can also supplement the embedding lithium capacity of height of silicon.It is this early in 2006
Silicon-carbon nucleocapsid is just obtained by way of being pyrolyzed silicon precursor, and under the current density of 100mA/g, capacity is 20
1189mAh/g can be maintained in a cycle.But as the increase of cycle-index, battery capacity and stability are but less managed
Think.
Invention content
The present invention is to solve the technical problems of the stability difference of existing silicon-carbon nucleocapsid lithium cell cathode material, and
A kind of preparation method of lithium battery silicon-carbon composite material is provided.
The preparation method of the lithium battery silicon-carbon composite material of the present invention, includes the following steps：
One, silicon powder is heat-treated in air atmosphere, carries out incomplete oxidation reaction, it is compound obtains Si-SiOx
Object；
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, nanoscale Si-SiOx compounds are distributed in water, surfactant is added, after adjusting pH value is 7.5-9,
It is in molar ratio by aldehyde monomer and phenol monomer (1.1~3.2)：The monomer for preparing phenolic resin is added to reactor by 1 ratio
In, it stirs evenly, is persistently stirred to react 16~25h at normal temperatures, complete the resin cladding of Si-SiOx compounds；
Four, the Si-SiOx compounds that resin coats are placed in the heating furnace of argon gas or nitrogen atmosphere, are 650 in temperature
DEG C~950 DEG C under conditions of carbonize 2h~9h, obtain carbon coating Si-SiOx compounds；
Five, SiO carbon coating Si-SiOx compounds being immersed in hydrofluoric acid solution in material removal2, cleaned after filtering
To neutral, drying, lithium battery silicon-carbon composite material is obtained.
The present invention is first heat-treated silica flour, carries out incomplete oxidation reaction at high temperature, and it is compound to obtain Si-SiOx
Object, then phenol monomer and aldehyde monomer are put into deionized water and mixed, synthesizes organic carbon matrix precursor, and by the Si- of preparation
SiOx compounds are added, and under weak basic condition, Surfactant CTAB are added, stirring is closed on the surface of Si-SiOx compounds
At the presoma of high-specific surface area phenolic aldehyde macromolecule resin coated Si, resin cladding is completed, then detaches gained carbon matrix precursor
It is dry, it is roasted under protective atmosphere and at specific temperature, SiOx decomposes, and obtains Si/SiO2 C coated core-shell knots
Structure finally removes SiO with hf etching2, finally obtain silicon-carbon silicon-carbon nucleocapsid anode material.
The silicon-carbon composite cathode material of the present invention has typical nucleocapsid, fully combine silicon the embedding lithium capacity of height and
The mechanical elasticity of the excellent mechanical performance of carbon and electric conductivity, carbon material can buffer the huge volume expansion of silicon, while high
Electronic conductivity can also supplement the embedding lithium capacity of height of silicon.The silicon-carbon composite cathode material has high specific capacity, and electric discharge for the first time is held
Amount is 800~1142mAh/g, and coulombic efficiency reaches 82%~91% for the first time, and coulombic efficiency and coulomb for the first time after 100 cycles
Efficiency is suitable, still can reach 84%~92%, the stability of cycle greatly improves.The method of the present invention is easy to operate, and raw material is easy
, it is easy to mass produce.It can be used for electrochemical energy field of material technology.
Description of the drawings
Fig. 1 is the principle schematic of the preparation process of the present invention；
Fig. 2 is the transmission electron microscope (TEM) of the Si/SiOx compounds by heat treatment process synthesis in embodiment 1
Figure；
Fig. 3 is the transmission electron microscope (TEM) of the silicon-carbon composite cathode material of lithium ion battery prepared in embodiment 1
Figure.
Specific implementation mode
Specific implementation mode one：The preparation method of the lithium battery silicon-carbon composite material of present embodiment, including it is following
Step：
One, silicon powder is heat-treated in air atmosphere, carries out incomplete oxidation reaction, it is compound obtains Si-SiOx
Object；
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, nanoscale Si-SiOx compounds are distributed in water, surfactant is added, after adjusting pH value is 7.5-9,
It is in molar ratio by aldehyde monomer and phenol monomer (1.1~3.2)：The monomer for preparing phenolic resin is added to reactor by 1 ratio
In, it stirs evenly, is persistently stirred to react 16~25h at normal temperatures, complete the resin cladding of Si-SiOx compounds；
Four, the Si-SiOx compounds that resin coats are placed in the heating furnace of argon gas or nitrogen atmosphere, are 650 in temperature
DEG C~950 DEG C under conditions of carbonize 2h~9h, obtain carbon coating Si-SiOx compounds；
Five, SiO carbon coating Si-SiOx compounds being immersed in hydrofluoric acid solution in material removal2, cleaned after filtering
To neutral, drying, lithium battery silicon-carbon composite material is obtained.
Specific implementation mode two：The present embodiment is different from the first embodiment in that the silicon powder in step 1 is to use
Pure silicon powder is obtained after pickling removal impurity；It is other same as the specific embodiment one.
Specific implementation mode three：Present embodiment pickling described unlike specific implementation mode two is to use quality hundred
Divide a concentration of 3%~12% hydrochloric acid soaking and stirring 1~6 hour；It is other to be identical with embodiment two.
Specific implementation mode four：Aldehyde in step 3 unlike one of present embodiment and specific implementation mode one to three
Monomer is formaldehyde, propionic aldehyde or 3-HPA；It is other identical as one of specific implementation mode one to three.
Specific implementation mode five：Phenol in step 3 unlike one of present embodiment and specific implementation mode one to four
Monomer is phenol, cresols or 2- hydroxyl phenols；It is other identical as one of specific implementation mode one to four.
Specific implementation mode six：It is adjusted in step 3 unlike one of present embodiment and specific implementation mode one to five
The ammonium hydroxide or sodium hydroxide solution that material used in pH value is a concentration of 0.1~5.5mol/L；Other and specific implementation mode one
It is identical to one of five.
Specific implementation mode seven：Table in step 3 unlike one of present embodiment and specific implementation mode one to six
Face activating agent is quaternary ammonium salt；A concentration of 0.3~3.5mol/L of surfactant；One of other and specific implementation mode one to six
It is identical.
Specific implementation mode eight：Table in step 3 unlike one of present embodiment and specific implementation mode one to seven
Face activating agent is cetyl trimethylammonium bromide (CTAB)；It is other identical as one of specific implementation mode one to seven.
Specific implementation mode nine：Tree in step 3 unlike one of present embodiment and specific implementation mode one to eight
Absolute ethyl alcohol is added in fat cladding operation, the addition of absolute ethyl alcohol is the 2%~5% of nanoscale Si-SiOx compound quality；
It is other identical as one of specific implementation mode one to eight.
In present embodiment, by the way that a small amount of absolute ethyl alcohol is added to increase the dispersibility of Si/SiOx compounds.
Specific implementation mode ten：Heat in step 1 unlike one of present embodiment and specific implementation mode one to nine
The temperature of processing is 750~850 DEG C, and heat treatment time is 6~8h.It is other identical as one of specific implementation mode one to nine.
Beneficial effects of the present invention are verified with following embodiment：
Embodiment 1：The preparation method of the lithium battery silicon-carbon composite material of the present embodiment carries out according to the following steps：
One, the salt acid soak that the silicon powder that 20g mass percent purities are 99.99% is 10% with mass percentage concentration is stirred
It after mixing 1 hour, filters out, is placed in Muffle furnace after dry to neutrality wash with distilled water, 750 are warming up under air atmosphere
DEG C keep 6h carry out incomplete oxidation reaction, obtain Si-SiOx compounds；
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, 8g nanoscale Si-SiOx compounds are distributed in 920mL deionized waters, 40mlCTAB solution is added and makees table
Face activating agent, after adding 4ml ammonium hydroxide adjusting pH value, 5g resorcinols are added in reactor, stir 6min, and 8ml matter is added
The formaldehyde that percentage concentration is 36% is measured, the condition for being 30 DEG C in temperature is persistently stirred to react 16h, places reaction liquid into centrifuge
5min is centrifuged with 10000r/min speed, gained solid formation is added deionized water and rinses after centrifugation, adjusts pH to neutrality, is placed in dry
The resin cladding of Si-SiOx compounds is completed in the 80 DEG C of drying of dry case；
Four, by resin coat Si-SiOx compounds be placed in high temperature process furnances, be passed through nitrogen and make protection gas, with 5 DEG C/
The heating rate 170min of min is warming up to 850 DEG C, and after constant temperature 120min, natural cooling obtains carbon coating Si-SiOx compounds；
Five, carbon coating Si-SiOx compounds are immersed in the HF solution that mass percentage concentration is 40%, are stirred to react
SiO in 20min material removals2, it filters after stratification, deionized water is added and cleans to pH to neutrality, it is dry, obtain lithium electricity
Pond silicon-carbon composite cathode material.
Fig. 2 is that the transmitted electron of the Si/SiOx compounds of the heat treatment process synthesis Jing Guo step 1 in the present embodiment 1 is aobvious
Micro mirror (TEM) figure；Figure it is seen that the Si/SiOx samples after oxidation have still maintained the flat of micron silicon raw material,
Dark is nano Si, and that light is SiOx, and SiOx is wrapped in nano Si, and the two is cross-linked with each other, and forms Si/SiOx composite woods
Material.
Fig. 3 is the transmission electron microscopy of the silicon-carbon composite cathode material of lithium ion battery prepared through step 5 in embodiment 1
Mirror (TEM) figure；From figure 3, it can be seen that a diameter of 50nm of nano silica fume, surface are all wrapped in the amorphous carbon layer of 10nm thickness,
It can be seen that apparent nucleocapsid.External carbon-coating not only individually separately wraps up silica flour, further through amorphous carbon
It is in electrical contact between layer, to ensure the independence between the integrality of composite material and nano silica fume.
The negative material of 1 gained of the present embodiment is subjected to assembling half-cell in the following manner：
1. lithium battery silicon-carbon composite material, PVDF and acetylene black powder are pressed 8 first:1:1 ratio is weighed and is mixed
It closes, after being put into mortar progress mechanical agitation 30min, obtains light black uniform powder；
2. NMP (N-Methyl pyrrolidone) is added into mortar, constantly it is stirred in the process, so that it is fully mixed
It closes, black paste that is sticky and having certain fluidity is obtained after continuously stirring 1h；
3. the slurry being stirred is placed on one piece of drying copper foil, slurry is coated uniformly on copper foil using automatic spray device
Surface, thickness are no more than 70 μm, the copper foil after coating are put into air dry oven, 80 DEG C of forced air drying 6h；
4. the copper foil after coating and drying to be washed into the pole piece of diameter 15mm using tablet press machine, and it is empty to rush several identical sizes
Copper-nickel alloy foil is put into togerther vacuum drying chamber, and 80 DEG C of vacuum drying 4h weigh and record blank copper foil quality after the completion of dry, empty
Copper-nickel alloy foil and the of poor quality of pole piece are multiplied by active material ratio, as active material quality；
5. the equipment such as pole piece, electrolyte and dry needle tubing, diaphragm are put into glove box, electrolyte is with methyl ethyl
Ester：Ethylene carbonate：The volume ratio of dimethyl carbonate is 1：1：1 mixing liquid is solvent, by 1mol L-1Concentration be added
LiPF6It is uniformly mixed and obtains.Half-cell is assembled in order, is lithium piece to electrode；
6. after half-cell is completed, being taken out from glove box, it is put into thermostatic constant wet chamber and stands 12h, electrolyte fully soaks
Every electrochemical property test can be carried out after profit.
It is tested using galvanostatic method, test equipment is that the blue electricity CT2001A in Wuhan tests system, test current density 100mA/
G, 0.01~1.5V of voltage range.100 performance tests recycled have been carried out for the half-cell made is made.
Embodiment 2：The preparation method of the lithium battery silicon-carbon composite material of the present embodiment carries out according to the following steps：
One, the silicon powder that 15g mass percent purities are 99.99% is placed in Muffle furnace, is warming up to 750 DEG C in air
It keeps 6h to carry out incomplete oxidation reaction, obtains Si-SiOx compounds；
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, 8g nanoscale Si-SiOx compounds are distributed in 920mL deionized waters, 40mlCTAB solution is added and makees table
Face activating agent, then sum it up 4ml ammonium hydroxide adjust pH value 8 after, 5g resorcinols are added in reactor, stir 6min, be added 8ml
The formaldehyde that mass percentage concentration is 36%, the condition for being 30 DEG C in temperature are persistently stirred to react 16h, place reaction liquid into centrifuge
In with 10000r/min speed centrifuge 5min, after centrifugation gained solid formation be added deionized water rinse, adjust pH to neutrality, be placed in
The resin cladding of Si-SiOx compounds is completed in 80 DEG C of drying of drying box；
Four, by resin coat Si-SiOx compounds be placed in high temperature process furnances, be passed through nitrogen and make protection gas, with 5 DEG C/
The heating rate 170min of min is warming up to 750 DEG C, and after constant temperature 120min, natural cooling obtains carbon coating Si-SiOx compounds；
Five, carbon coating Si-SiOx compounds are immersed in the HF solution that mass percentage concentration is 40%, are stirred to react
SiO in 20min material removals2, it filters after stratification, deionized water is added and cleans to pH to neutrality, it is dry, obtain lithium electricity
Pond silicon-carbon composite cathode material.
By battery assembly method assembled battery described in example 1, tested using identical electrochemical test method.
Embodiment 3：The preparation method of the lithium battery silicon-carbon composite material of the present embodiment carries out according to the following steps：
One, the silicon powder that 20g mass percent purities are 99.99% is placed in Muffle furnace, 850 is warming up under air atmosphere
DEG C keep 7h carry out incomplete oxidation reaction, obtain Si-SiOx compounds
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, 8g nanoscale Si-SiOx compounds are distributed in 920mL deionized waters, 40mlCTAB solution is added and makees table
Face activating agent, then sum it up 10ml ammonium hydroxide adjust pH value after, 5g resorcinols are added in reactor, stir 6min, be added 8ml
The formaldehyde that mass percentage concentration is 36%, the condition for being 30 DEG C in temperature are persistently stirred to react 16h, place reaction liquid into centrifuge
In with 10000r/min speed centrifuge 5min, after centrifugation gained solid formation be added deionized water rinse, adjust pH to neutrality, be placed in
The resin cladding of Si-SiOx compounds is completed in 80 DEG C of drying of drying box；
Four, by resin coat Si-SiOx compounds be placed in high temperature process furnances, be passed through nitrogen and make protection gas, with 5 DEG C/
The heating rate 170min of min is warming up to 850 DEG C, and after constant temperature 120min, natural cooling obtains carbon coating Si-SiOx compounds；
Five, carbon coating Si-SiOx compounds are immersed in the HF solution that mass percentage concentration is 40%, are stirred to react
SiO in 20min material removals2, it filters after stratification, deionized water is added and cleans to pH to neutrality, it is dry, obtain lithium electricity
Pond silicon-carbon composite cathode material.
By battery assembly method assembled battery described in example 1, tested using identical electrochemical test method.
Embodiment 4：The preparation method of the lithium battery silicon-carbon composite material of the present embodiment carries out according to the following steps：
One, the silicon powder that 20g mass percent purities are 99.99% is placed in Muffle furnace, 750 is warming up under air atmosphere
DEG C keep 6h carry out incomplete oxidation reaction, obtain Si-SiOx compounds
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, 8g nanoscale Si-SiOx compounds are distributed in 920mL deionized waters, 60mlCTAB solution is added and makees table
Face activating agent, then sum it up 10ml ammonium hydroxide adjust pH value after, 5g resorcinols are added in reactor, stir 6min, be added 8ml
The formaldehyde that mass percentage concentration is 36%, the condition for being 30 DEG C in temperature are persistently stirred to react 16h, place reaction liquid into centrifuge
In with 10000r/min speed centrifuge 5min, after centrifugation gained solid formation be added deionized water rinse, adjust pH to neutrality, be placed in
The resin cladding of Si-SiOx compounds is completed in 80 DEG C of drying of drying box；
Four, by resin coat Si-SiOx compounds be placed in high temperature process furnances, be passed through nitrogen and make protection gas, with 5 DEG C/
The heating rate 170min of min is warming up to 850 DEG C, and after constant temperature 120min, natural cooling obtains carbon coating Si-SiOx compounds；
Five, carbon coating Si-SiOx compounds are immersed in the HF solution that mass percentage concentration is 40%, are stirred to react
SiO in 20min material removals2, it filters after stratification, deionized water is added and cleans to pH to neutrality, it is dry, obtain lithium electricity
Pond silicon-carbon composite cathode material.
By battery assembly method assembled battery described in example 1, tested using identical electrochemical test method.
Embodiment 5：The preparation method of the lithium battery silicon-carbon composite material of the present embodiment carries out according to the following steps：
One, the salt acid soak that the silicon powder that 20g mass percent purities are 99.99% is 10% with mass percentage concentration is stirred
It after mixing 1 hour, filters out, is placed in Muffle furnace after dry to neutrality wash with distilled water, 750 are warming up under air atmosphere
DEG C keep 6h carry out incomplete oxidation reaction, obtain Si-SiOx compounds
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, 8g nanoscale Si-SiOx compounds are distributed in 920mL deionized waters, 2ml absolute ethyl alcohols are added, then add
Enter 40mlCTAB solution and make surfactant, then after adding 4ml ammonium hydroxide to adjust pH value, 10g resorcinols are added in reactor,
6min is stirred, the formaldehyde that 15ml mass percentage concentrations are 36% is added, 16h is persistently stirred to react in 30 DEG C of condition of temperature, it will
Reaction solution is placed in a centrifuge centrifuges 5min with 10000r/min speed, and gained solid formation is added deionized water and rinses after centrifugation,
PH is adjusted to neutrality, 80 DEG C of drying of drying box is placed in, completes the resin cladding of Si-SiOx compounds；
Four, by resin coat Si-SiOx compounds be placed in high temperature process furnances, be passed through nitrogen and make protection gas, with 5 DEG C/
The heating rate 170min of min is warming up to 850 DEG C, and after constant temperature 120min, natural cooling obtains carbon coating Si-SiOx compounds；
Five, carbon coating Si-SiOx compounds are immersed in the HF solution that mass percentage concentration is 40%, are stirred to react
SiO in 20min material removals2, it filters after stratification, deionized water is added and cleans to pH to neutrality, it is dry, obtain lithium electricity
Pond silicon-carbon composite cathode material.
By battery assembly method assembled battery described in example 1, tested using identical electrochemical test method.
After the lithium ion battery negative material prepared in Examples 1 to 5 is carried out electrochemical property test, result is carried out
Comparison, as shown in table 1 below, from test result it can be seen that lithium ion battery silicon-carbon Compound Negative prepared by the method for Examples 1 to 5
Pole material has higher specific capacity and good cycle efficieny.
Table 1：Lithium ion battery silicon-carbon cathode chemical property
From the data of table 1 as can be seen, coulombic efficiency is suitable with coulombic efficiency for the first time after 100 cycles, 84% still can reach
~92%, the stability of cycle substantially increases.
Claims (10)
1. a kind of preparation method of lithium battery silicon-carbon composite material, it is characterised in that this approach includes the following steps：
One, silicon powder is heat-treated in air atmosphere, carries out incomplete oxidation reaction, obtains Si-SiOx compounds；
Two, Si-SiOx compounds are subjected to crushing grinding and sieved, obtain nanoscale Si-SiOx compounds；
Three, nanoscale Si-SiOx compounds are distributed in water, surfactant are added, after adjusting pH value is 7.5-9, by aldehyde
Monomer and phenol monomer are (1.1~3.2) in molar ratio：The monomer for preparing phenolic resin is added in reactor by 1 ratio, is stirred
It mixes uniformly, is persistently stirred to react 16~25h at normal temperatures, complete the resin cladding of Si-SiOx compounds；
Four, by resin coat Si-SiOx compounds be placed in the heating furnace of argon gas or nitrogen atmosphere, temperature be 650 DEG C~
2h~9h is carbonized under conditions of 950 DEG C, obtains carbon coating Si-SiOx compounds；
Five, SiO carbon coating Si-SiOx compounds being immersed in hydrofluoric acid solution in material removal2, cleaning is into after filtering
Property, drying, obtain lithium battery silicon-carbon composite material.
2. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 1, it is characterised in that step
Silicon powder in one is to obtain pure silicon powder after removing impurity with pickling.
3. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 2, it is characterised in that described
Pickling be 3%~12% with mass percentage concentration hydrochloric acid soaking and stirring 1~6 hour.
4. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 1 or 2, it is characterised in that step
Aldehyde monomer in rapid three is formaldehyde, propionic aldehyde or 3-HPA.
5. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 1 or 2, it is characterised in that step
Phenol monomer in rapid three is phenol, cresols or 2- hydroxyl phenols.
6. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 1 or 2, it is characterised in that step
Ammonium hydroxide or sodium hydroxide solution that the material used in pH value is a concentration of 0.1~5.5mol/L are adjusted in rapid three.
7. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 1 or 2, it is characterised in that step
Surfactant in rapid three is quaternary ammonium salt；A concentration of 0.3~3.5mol/L of surfactant.
8. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 7, it is characterised in that described
Quaternary ammonium salt be cetyl trimethylammonium bromide.
9. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 7, it is characterised in that step
Absolute ethyl alcohol is added in resin cladding operation in three, the addition of absolute ethyl alcohol is nanoscale Si-SiOx compound quality
2%~5%.
10. a kind of preparation method of lithium battery silicon-carbon composite material according to claim 1 or 2, it is characterised in that
The temperature being heat-treated in step 1 is 750~850 DEG C, and heat treatment time is 6~8h.
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