CN109755546A - A kind of preparation method of lithium-ion-power cell silicon based composite material - Google Patents
A kind of preparation method of lithium-ion-power cell silicon based composite material Download PDFInfo
- Publication number
- CN109755546A CN109755546A CN201910175785.9A CN201910175785A CN109755546A CN 109755546 A CN109755546 A CN 109755546A CN 201910175785 A CN201910175785 A CN 201910175785A CN 109755546 A CN109755546 A CN 109755546A
- Authority
- CN
- China
- Prior art keywords
- silicon
- composite material
- nano
- plastics
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods of lithium-ion-power cell silicon based composite material, belong to lithium ion battery negative material field, it include: using nano-silicon, plastics and montmorillonite as raw material, heavy metallic salt is added as catalyst, extrusion granulation is carried out after raw material is mixed under melting condition, obtains nano-silicon/plastic/montmorillonite composite material；Nonionic surfactant and cationic surfactant are added in hydrochloric acid solution, obtain mixed solution, nano-silicon/plastic/montmorillonite composite material is added in mixed solution, solgel reaction is carried out, obtains nano-silicon/plastics/silicon dioxide composite material；By nano-silicon/plastics/silicon dioxide composite material carry out carbon thermal reduction to get.The present invention is utilized the heavy metallic salt inducing catalysis plastics and catalyzed graphitization the characteristics of, is used as carbon source by means of plastics, realizes that low temperature graphitization and graphitized carbon uniformly coat silicon nanoparticle, the chemical property of raising silicium cathode material.
Description
Technical field
The invention belongs to lithium ion battery negative material fields, are related to a kind of lithium-ion-power cell silicon based composite material
Preparation method.
Background technique
One of system is stored and transmitted as most promising electrochemical energy, lithium ion battery is widely used to portable
Formula electronic equipment and electric car and aviation field, and the performance of negative electrode material is to influence the service life of lithium ion battery, capacity,
One of principal elements of performances such as safety.Nowadays, most widely used lithium-ion negative pole is graphite material, but its theoretical capacity
Only 372mA h g-1, it is difficult to meet the further development of lithium ion battery, therefore, exploring has higher capacity and good circulation
The substitution negative electrode material of stability is very important for the development of the high power density of lithium ion battery.Silicium cathode is due to it
Theoretical capacity (the Li at room temperature of superelevation15Si4For 3579mA h g-1), it is abundant deposit and relatively low removal lithium embedded current potential (<
0.5 couple of Li/Li+) and cause more and more to pay close attention to.But ultralow conductivity existing for silicium cathode, enormousness when lithiumation
The problem of expansion and the formation of unstable solid-electrolyte interphace (SEI), it is made to be difficult to commercial applications.
Huge volume expansion problem and silicium cathode material is improved to reduce silicium cathode material during removal lithium embedded
Electric conductivity, has carried out extensive research at present, and Main way is the preparation and silicon based composite material preparation of nano material
Two aspects, for example, patent CN106935815A discloses a kind of preparation method of Si-C composite material, are related to silicon-carbon cathode material
Synthesis field, this method after being placed in metallic silicon in graphite crucible after evenly mixing according to a certain percentage with graphite powder by being put into
Heated in closed stove, by adjusting the preparation of furnace kiln inner pressure control composite material in constant temperature insulating process, is obtained
To Si-C composite material；Patent CN107394122A discloses a kind of preparation method of compound silicon-carbon cathode material, passes through preparation
Out after silica-rich material, polyacrylonitrile is dissolved in organic solution, the silica-rich material of appropriate quality is then added, by abundant ball
After mill is stirred, finally cooperate with electrospinning process, is carried out using the organic spinning object of macromolecule as carbon source compound；Patent
CN107611369A discloses a kind of lithium-ion battery silicon-carbon anode material and preparation method thereof, passes through silicon or its oxide table
Surface treatment, roasting are broken up, and are then merged, are coated with charcoal micro mist and organic carbon source, finally carry out carbonizing obtained silicon-carbon cathode material.
The method of modifying used in above-mentioned patent is that silicon is embedded into carbon matrix, to effectively alleviate huge volume
Expansion improves the electronic conductivity of buffering and conductive matrices.However, with carbon matrix is compound needs to solve silicon materials in matrix
The problem of dispersibility and stability, it is also desirable to which consideration prepares the economic cost problem of composite material.Therefore, there is an urgent need to a kind of letters
Single, effective and feasible method prepares silicon based composite material.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of stable structure, good dispersion, electrochemistries
The preparation method of excellent, the low-cost lithium-ion-power cell silicon based composite material of energy.
The preparation method of this lithium-ion-power cell silicon based composite material provided by the invention, comprising:
Using nano-silicon, plastics and montmorillonite as raw material, be added heavy metallic salt be used as catalyst, by the raw material mixing after
Extrusion granulation is carried out under melting condition, obtains nano-silicon/plastic/montmorillonite composite material；
Nonionic surfactant and cationic surfactant are added in hydrochloric acid solution, mixed solution is obtained, it will
Nano-silicon/plastic/montmorillonite composite material is added in mixed solution, carry out solgel reaction, obtain nano-silicon/plastics/
Silicon dioxide composite material；
Nano-silicon/plastics/silicon dioxide composite material is subjected to carbon thermal reduction, it is sub- to obtain nano-silicon/graphitized carbon/oxidation
Silicon composite (Si/GC/SiOx), i.e., the described lithium-ion-power cell silicon based composite material.
Preferably, the nano-silicon, plastics and the mass ratio of montmorillonite are (1~5): (20~40): (2~10).
Preferably, the partial size of the nano-silicon is 100~500nm.
Preferably, the heavy metallic salt is one of nickel salt, cobalt salt, molysite, manganese salt or a variety of, heavy metallic salt adds
Dosage is 1~5wt% of raw material.
Further preferably, the nickel salt is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of；The cobalt
Salt is one of cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride or a variety of；The molysite be ferric nitrate, ferric acetate, ferric sulfate,
One of iron chloride is a variety of；The manganese salt is one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride or a variety of.
Preferably, the nonionic surfactant is Triton X2100, one in OP-10, TX-10, NP-8.6
Kind is a variety of, and the additive amount of the nonionic surfactant is 5~10wt% of nano-silicon/plastic/montmorillonite composite material.
Preferably, the cationic surfactant is cetyl trimethyl season ammonium bromide, octadecyldimethyl
Benzyl season ammonium chloride, tri alkyl ammomium chloride, one of trialkyl methyl ammonium chloride or a variety of, the cationic surfactant
Additive amount be 15~20wt% of nano-silicon/plastic/montmorillonite composite material.
Preferably, the concentration of hydrochloric acid is 1~5mol/L, hydrochloric acid and nano-silicon/plastic/montmorillonite composite material mole
Than for (1~10): 1.
Preferably, the plastics are one of polypropylene, polyethylene, polystyrene or a variety of.
Further preferably, the preparation method of the lithium-ion-power cell silicon based composite material, comprising the following steps:
(1) after mixing by nano-silicon, plastics, heavy metallic salt and montmorillonite, it is placed in double screw extruder, control is molten
Melt condition, setting screw speed and processing temperature under carry out extruding pelletization, be cooled to room temperature taking-up, obtain nano-silicon/plastics/
Montmorillonite composite material；
(2) nonionic surfactant of predetermined amount and cationic surfactant are dissolved in hydrochloric acid solution, until surface
Activating agent all dissolves and after solution change clarification, is added with stirring nano-silicon/plastic/montmorillonite composite material obtained by step (1),
Stir 0.5~2h, at room temperature, still aging 10~20h is then centrifuged for, and is washed, dry, obtain nano-silicon/plastics/
Silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material obtained by step (2) is placed in tube furnace to carry out first segment lazy
Property atmosphere sintering, inert atmosphere be selected from one or more of helium, argon gas, neon, nitrogen mixed gas, the liter of heat treatment
Warm system is 1~10 DEG C/min, and holding temperature is 500~800 DEG C, and soaking time is 2~12h, obtains one-stage sintering product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is selected from hydrogen and helium, argon gas, neon
The mixed gas of one or more of gas, nitrogen, the temperature increasing schedule of heat treatment are 5~20 DEG C/min, holding temperature is 900~
1500 DEG C, soaking time is 2~12h, and cooled to room temperature after the completion of sintering obtains institute by product by broken and classification
State lithium-ion-power cell silicon based composite material.
Further preferably, in the step (1), hybrid mode is using one in mechanical stirring, mechanical ball mill, mechanical lapping
Kind is a variety of.
Further preferably, in the step (1), screw speed is 30~100rpm, and mixing time is 6~10h；Processing temperature
Degree is 220~270 DEG C.
Further preferably, in the step (3), the crumbling method is using mechanical crushing or air-flow crushing, the classification
Mode uses vibrosieve or air current classifying.
Further preferably, in the step (3), first segment inert atmosphere sintering, the temperature increasing schedule of heat treatment is 1~
5 DEG C/min, holding temperature is 600~700 DEG C, and soaking time is 5~10h.
Further preferably, in the step (3), second segment reducing atmosphere sintering, the temperature increasing schedule of heat treatment is 5~
10 DEG C/min, holding temperature is 1000~1200 DEG C, and soaking time is 5~8h.
The present invention also provides a kind of nano-silicon/graphitized carbon/oxidation Asia silicon composite, the sub- silicon of the oxidation is cladding
Layer, nano-silicon and graphitized carbon are matrix, and the nano-silicon/graphitized carbon/oxidation Asia silicon composite forms core-shell structure, should
The partial size of composite material is 10~30um, and the mass ratio of nano-silicon and graphitized carbon is 1:(1~10), the content for aoxidizing sub- silicon is
2~5wt% of nano-silicon/graphitized carbon/oxidation Asia silicon composite.
The present invention also provides a kind of applications of the nano-silicon/graphitized carbon/oxidation Asia silicon composite, by the nanometer
Silicon/graphitized carbon/oxidation Asia silicon composite is applied to lithium ion battery as negative electrode material.
The preparation method of lithium-ion-power cell silicon based composite material of the present invention, by heavy metallic salt and Meng Tuo
Under the conditions of existing for native, plastics generate knitting wool spherical structure under melt temperature, by the way that heavy metallic salt is added to be catalyzed induction plastics
Linear fiber tubular structure, and the feature poor using montmorillonite wetability in molten plastic are generated, plastic melt is inhibited
Agglomeration in process of setting prepares the knitting wool variole that the nano-silicon coated by montmorillonite is uniformly mixed with plastic optical fibre pipe
Grain；Silicate contained in montmorillonite is as the raw material for preparing silica, by forming two after the processing of collosol and gel again
The knitting wool ball particle that the nano-silicon of silica cladding is uniformly mixed with plastic optical fibre pipe, finally obtains Si/GC/ through carbon thermal reduction again
SiOxComposite material.
Compared with the existing technology, the present invention has following advantageous effects:
(1) preparation method of lithium-ion-power cell silicon based composite material of the present invention, lures using in heavy metallic salt
The characteristics of leading catalysis plastics and catalyzed graphitization realizes low temperature graphitization and graphitized carbon by means of plastics as carbon source
Uniformly cladding silicon nanoparticle, not only can be improved the conductivity of silicon, silicium cathode can also be inhibited in the volume of charge and discharge process
Expansion prevents the generation of silicium cathode material pulverizing problem, improves the chemical property of silicium cathode material.
(2) preparation method of lithium-ion-power cell silicon based composite material of the present invention, passes through collosol and gel and carbon
Thermal reduction processing, the characteristic for taking full advantage of the fixedly separated molten plastic of montmorillonite prepare knitting wool ball particle, and montmorillonite is as silicon
Source synthesis aoxidizes sub- silicon, realizes the uniform cladding for aoxidizing sub- silicon, prepares Si/GC/SiOxStabilization can be generated in composite material
Solid-electrolyte interphace film (SEI film), to further improve the chemical property of the negative electrode material.
(3) preparation method of lithium-ion-power cell silicon based composite material of the present invention, with nanometer cheap and easy to get
Silicon, plastics are raw material, and plastics can be the rubbish of recycling, and carburizing temperature is low, can not only solve point of the silicon materials in matrix
The problem of dissipating property and stability, and low raw-material cost, also can avoid general silicon-carbon cathode material by high temperature graphitization institute
The problem that bring mass energy consumes and economic cost is high.
(4) nano-silicon/graphitized carbon of the present invention/oxidation Asia silicon composite, forms stable core-shell structure, dispersion
Property is good, and capacity height, has extended cycle life at good rate capability, as high performance lithium dynamical battery Si/GC/SiOxComposite material
It has broad application prospects.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of lithium-ion-power cell silicon based composite material of the present invention.
Fig. 2 is Si/GC/SiO of the present inventionxThe structural schematic diagram of composite material.
Fig. 3 is Si/GC/SiO prepared by embodiment 4xThe XRD diagram of composite material.
Fig. 4 is Si/GC/SiO prepared by embodiment 4xThe transmission electron microscope picture (TEM) of composite material.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Experimental method described in following embodiments is unless otherwise specified conventional method, the reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
A kind of preparation method of lithium-ion-power cell silicon based composite material of the present invention, process flow Fig. 1, including such as
Lower step:
(1) 1g nano-silicon, 50g plastics (polypropylene, PP), 0.56g nickel chloride and 5g montmorillonite are passed through into mechanical lapping
Mode mixes after the meeting, is placed in double screw extruder, controls melting condition, and the screw speed for controlling extruder stirs for 30rpm
6h is mixed, the processing temperature for controlling extruder is 220 DEG C, and extruding pelletization is cooled to room temperature taking-up, and it is de- to obtain nano-silicon/plastics/illiteracy
Soil composite material；
(2) Triton X2100 and 1.5g the cetyl trimethyl season ammonium bromide of 1.5ml is dissolved in 100ml1mol/L
Hydrochloric acid solution, until surfactant all dissolution and solution become clarification after, be added with stirring 0.1mol nano-silicon/plastics/illiteracy
De- soil composite material, the molar ratio of control n (HCl)/n (nano-silicon/plastic/montmorillonite composite material) are 1:1, stir 0.5h,
At room temperature, still aging 10h, is then centrifuged for, and washs, dry, obtains nano-silicon/plastics/silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material is placed in progress first segment inert atmosphere sintering in tube furnace,
Inert atmosphere is helium, and the temperature increasing schedule of heat treatment is 1 DEG C/min, and holding temperature is 500 DEG C, and soaking time is 12h, obtains one
Section sintered product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and helium,
The temperature increasing schedule of heat treatment is 5 DEG C/min, and holding temperature is 1000 DEG C, and soaking time is 8h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains Si/GC/SiO by room temperaturexComposite material.
By 1 gained Si/GC/SiO of embodimentxComposite material is being gone with acetylene black and sodium alginate by the mass ratio of 6:2:2
Slurry is made in ion aqueous medium, is coated on copper foil, 120 DEG C of vacuum drying, with lithium piece be to electrode, polypropylene screen be every
Film, electrolyte are 1ML LiPF6/ (EC:DEC=1:1)+10%FEC, battery case model 2025 are filled with 0.2C current density
It discharges (1C=4200mA/g), cycle life test is carried out in the voltage range of 0.01~1.2V.
Embodiment 2
A kind of preparation method of lithium-ion-power cell silicon based composite material of the present invention, includes the following steps:
(1) 1g nano-silicon, 10g plastics (polypropylene, PP), 0.13g nickel sulfate and 2g montmorillonite are passed through into mechanical lapping
Mode mixes after the meeting, is placed in double screw extruder, controls melting condition, and the screw speed for controlling extruder stirs for 100rpm
10h is mixed, the processing temperature for controlling extruder is 270 DEG C, and extruding pelletization is cooled to room temperature taking-up, obtains nano-silicon/plastics/illiteracy
De- soil composite material；
(2) OP-10 the and 1g tri alkyl ammomium chloride of 1ml is dissolved in the hydrochloric acid solution of 200ml 5mol/L, until surface is living
Property agent after all dissolution and solution become clarification, be added with stirring 0.1mol nano-silicon/plastic/montmorillonite composite material, control n
(HCl) molar ratio of/n (nano-silicon/plastic/montmorillonite composite material) is 10:1, stirs 2h, at room temperature, is stood old
Change 20h, be then centrifuged for, washs, it is dry, obtain nano-silicon/plastics/silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material is placed in progress first segment inert atmosphere sintering in tube furnace,
Inert atmosphere is nitrogen, and the temperature increasing schedule of heat treatment is 5 DEG C/min, and holding temperature is 700 DEG C, and soaking time is 2h, obtains one
Section sintered product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and nitrogen,
The temperature increasing schedule of heat treatment is 10 DEG C/min, and holding temperature is 1200 DEG C, and soaking time is 5h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains the Si/GC/SiO by room temperaturexComposite material.
By 2 gained Si/GC/SiO of embodimentxComposite material prepares electrode, assembled battery by identical method in embodiment 1
And test performance.
Embodiment 3
A kind of preparation method of lithium-ion-power cell silicon based composite material of the present invention, includes the following steps:
(1) 1g nano-silicon, 25g plastics (polypropylene, PP), 0.29g nickel acetate and 3g montmorillonite are passed through into mechanical lapping
Mode mixes after the meeting, is placed in double screw extruder, controls melting condition, and the screw speed for controlling extruder stirs for 50rpm
8h is mixed, the processing temperature for controlling extruder is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up, and it is de- to obtain nano-silicon/plastics/illiteracy
Soil composite material；
(2) NP-8.6 the and 2g trialkyl methyl ammonium chloride of 2ml is dissolved in the hydrochloric acid solution of 200ml 3mol/L, until table
Face activating agent all dissolves and after solution change clarification, is added with stirring 0.15mol nano-silicon/plastic/montmorillonite composite material, controls
The molar ratio of n (HCl)/n (nano-silicon/plastic/montmorillonite composite material) processed is 4:1, stirs 1h, at room temperature, is stood
It is aged 15h, is then centrifuged for, is washed, it is dry, obtain nano-silicon/plastics/silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material is placed in progress first segment inert atmosphere sintering in tube furnace,
Inert atmosphere is argon gas, and the temperature increasing schedule of heat treatment is 2 DEG C/min, and holding temperature is 650 DEG C, and soaking time is 8h, obtains one
Section sintered product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and argon gas,
The temperature increasing schedule of heat treatment is 6 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains the Si/GC/SiO by room temperaturexComposite material.
By 3 gained Si/GC/SiO of embodimentxComposite material prepares electrode, assembled battery by identical method in embodiment 1
And test performance.
Embodiment 4
A kind of preparation method of lithium-ion-power cell silicon based composite material of the present invention, includes the following steps:
(1) 1g nano-silicon, 25g plastics (polypropylene, PP), 0.29g manganese acetate and 3g montmorillonite are passed through into mechanical lapping
Mode mixes after the meeting, is placed in double screw extruder, controls melting condition, and the screw speed for controlling extruder stirs for 50rpm
8h is mixed, the processing temperature for controlling extruder is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up, and it is de- to obtain nano-silicon/plastics/illiteracy
Soil composite material；
(2) by the TX-10 of 2ml and 2g octadecyl dimethyl benzyl season chloride leach in the salt of 200ml3mol/L
Acid solution is added with stirring 0.15mol nano-silicon/plastic/montmorillonite until surfactant all dissolves and after solution change clarification
Composite material, the molar ratio of control n (HCl)/n (nano-silicon/plastic/montmorillonite composite material) are 4:1,1h are stirred, in room temperature
Under the conditions of, still aging 15h is then centrifuged for, and is washed, and it is dry, obtain nano-silicon/plastics/silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material is placed in progress first segment inert atmosphere sintering in tube furnace,
Inert atmosphere is neon, and the temperature increasing schedule of heat treatment is 2 DEG C/min, and holding temperature is 650 DEG C, and soaking time is 8h, obtains one
Section sintered product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and neon,
The temperature increasing schedule of heat treatment is 6 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains the Si/GC/SiO by room temperaturexComposite material.
By 4 gained Si/GC/SiO of embodimentxComposite material prepares electrode, assembled battery by identical method in embodiment 1
And test performance.
Embodiment 5
A kind of preparation method of lithium-ion-power cell silicon based composite material of the present invention, includes the following steps:
(1) 1g nano-silicon, 25g plastics (polypropylene, PP), 0.29g cobalt acetate and 3g montmorillonite are passed through into mechanical lapping
Mode mixes after the meeting, is placed in double screw extruder, controls melting condition, and the screw speed for controlling extruder stirs for 50rpm
8h is mixed, the processing temperature for controlling extruder is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up, and it is de- to obtain nano-silicon/plastics/illiteracy
Soil composite material；
(2) hydrochloric acid for the cetyl trimethyl season ammonium bromide of the OP-10 of 2ml and 2g being dissolved in 200ml 3mol/L is molten
It is compound to be added with stirring 0.15mol nano-silicon/plastic/montmorillonite until surfactant all dissolves and after solution change clarification for liquid
Material, the molar ratio of control n (HCl)/n (nano-silicon/plastic/montmorillonite composite material) are 4:1,1h are stirred, in room temperature condition
Under, still aging 15h is then centrifuged for, and is washed, and it is dry, obtain nano-silicon/plastics/silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material is placed in progress first segment inert atmosphere sintering in tube furnace,
Inert atmosphere is argon gas, and the temperature increasing schedule of heat treatment is 2 DEG C/min, and holding temperature is 650 DEG C, and soaking time is 8h, obtains one
Section sintered product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and argon gas,
The temperature increasing schedule of heat treatment is 6 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains the Si/GC/SiO by room temperaturexComposite material.
By 5 gained Si/GC/SiO of embodimentxComposite material prepares electrode, assembled battery by identical method in embodiment 1
And test performance.
Embodiment 6
A kind of preparation method of lithium-ion-power cell silicon based composite material of the present invention, includes the following steps:
(1) 1g nano-silicon, 25g plastics (polyethylene, PE), 0.29g iron chloride and 3g montmorillonite are passed through into mechanical lapping
Mode mixes after the meeting, is placed in double screw extruder, controls melting condition, and the screw speed for controlling extruder stirs for 50rpm
8h is mixed, the processing temperature for controlling extruder is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up, and it is de- to obtain nano-silicon/plastics/illiteracy
Soil composite material；
(2) TX-10 the and 2g trialkyl methyl ammonium chloride of 2ml is dissolved in the hydrochloric acid solution of 200ml 3mol/L, until table
Face activating agent all dissolves and after solution change clarification, is added with stirring 0.15mol nano-silicon/plastic/montmorillonite composite material, controls
The molar ratio of n (HCl)/n (nano-silicon/plastic/montmorillonite composite material) processed is 4:1, stirs 1h, at room temperature, is stood
It is aged 15h, is then centrifuged for, is washed, it is dry, obtain nano-silicon/plastics/silicon dioxide composite material；
(3) nano-silicon/plastics/silicon dioxide composite material is placed in progress first segment inert atmosphere sintering in tube furnace,
Inert atmosphere is argon gas, and the temperature increasing schedule of heat treatment is 2 DEG C/min, and holding temperature is 650 DEG C, and soaking time is 8h, obtains one
Section sintered product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and argon gas,
The temperature increasing schedule of heat treatment is 6 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains the Si/GC/SiO by room temperaturexComposite material.
By 6 gained Si/GC/SiO of embodimentxComposite material prepares electrode, assembled battery by identical method in embodiment 1
And test performance.
Comparative example 1
(1) 1g nano-silicon, 25g plastics (PP) and 3g montmorillonite are mixed after the meeting by way of mechanical lapping, is placed in
In double screw extruder, melting condition is controlled, the screw speed for controlling extruder is that 50rpm stirs 8h, controls adding for extruder
Work temperature is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up；
(2) NP-8.6 the and 2g trialkyl methyl ammonium chloride of 2ml is dissolved in the hydrochloric acid solution of 200ml 3mol/L, until table
The step of face activating agent all dissolves and after solution change clarification, is added with stirring 0.15mol (1) resulting material, control n (HCl)/
The molar ratio of n (material) is 4:1, stirs 1h, and at room temperature, still aging 15h is then centrifuged for, and is washed, dry；
(3) step (2) resulting material is placed in progress first segment inert atmosphere sintering in tube furnace, inert atmosphere is argon
Gas, the temperature increasing schedule of heat treatment are 2 DEG C/min, and holding temperature is 650 DEG C, and soaking time is 8h, obtains one-stage sintering product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and argon gas,
The temperature increasing schedule of heat treatment is 6 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains silicon based composite material by room temperature.
1 gained silicon based composite material of comparative example is prepared into electrode, assembled battery and test by identical method in embodiment 1
Performance.
Comparative example 2
(1) 1g nano-silicon, 25g plastics (PP) and 0.26g nickel acetate are mixed after the meeting by way of mechanical lapping, is set
In double screw extruder, melting condition is controlled, the screw speed for controlling extruder is that 50rpm stirs 8h, controls extruder
Processing temperature is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up；
(2) NP-8.6 the and 2g trialkyl methyl ammonium chloride of 2ml is dissolved in the hydrochloric acid solution of 200ml 3mol/L, until table
The step of face activating agent all dissolves and after solution change clarification, is added with stirring 0.15mol (1) resulting material, control n (HCl)/
The molar ratio of n (material) is 4:1, stirs 1h, and at room temperature, still aging 15h is then centrifuged for, and is washed, dry；
(3) step (2) resulting material is placed in progress first segment inert atmosphere sintering in tube furnace, inert atmosphere is argon
Gas, the temperature increasing schedule of heat treatment are 2 DEG C/min, and holding temperature is 650 DEG C, and soaking time is 8h, obtains one-stage sintering product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and argon gas,
The temperature increasing schedule of heat treatment is 6 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains silicon based composite material by room temperature.
2 gained silicon based composite material of comparative example is prepared into electrode, assembled battery and test by identical method in embodiment 1
Performance.
Comparative example 3
(1) 1g nano-silicon, 25g plastics (PP), 0.29g nickel acetate and 3g montmorillonite are mixed by way of mechanical lapping
After the meeting, it is placed in double screw extruder, controls melting condition, the screw speed for controlling extruder is that 50rpm stirs 8h, control
The processing temperature of extruder is 250 DEG C, and extruding pelletization is cooled to room temperature taking-up；
(2) NP-8.6 the and 2g trialkyl methyl ammonium chloride of 2ml is dissolved in the hydrochloric acid solution of 200ml 3mol/L, until table
The step of face activating agent all dissolves and after solution change clarification, is added with stirring 0.15mol (1) resulting material, control n (HCl)/
The molar ratio of n (material) is 4:1, stirs 1h, and at room temperature, still aging 15h is then centrifuged for, and is washed, dry；
(3) step (2) resulting material is placed in tube furnace and is sintered, sintering atmosphere is the mixed of hydrogen and argon gas
Gas is closed, the temperature increasing schedule of heat treatment is 5 DEG C/min, and holding temperature is 1100 DEG C, and soaking time is 6h, natural after the completion of sintering
It is cooled to room temperature, product is passed through into Mechanical Crushing and vibration separation, obtains silicon based composite material.
3 gained silicon based composite material of comparative example is prepared into electrode, assembled battery and test by identical method in embodiment 1
Performance.
Comparative example 4
(1) 1g nano-silicon, 10g plastics (PP), 0.1g nickel acetate and 10g montmorillonite are mixed by way of mechanical lapping
After the meeting, it is placed in double screw extruder, controls melting condition, the screw speed for controlling extruder is that 20rpm stirs 2h, control
The processing temperature of extruder is 200 DEG C, and extruding pelletization is cooled to room temperature taking-up；
(2) NP-8.6 the and 5g trialkyl methyl ammonium chloride of 5ml is dissolved in the hydrochloric acid solution of 100ml 0.5mol/L, until
The step of surfactant all dissolves and after solution change clarification, is added with stirring 0.5mol (1) resulting material, controls n
(HCl) molar ratio of/n (material) is 1:10, stirs 5h, and at room temperature, still aging 5h is then centrifuged for, and is washed, and is done
It is dry；
(3) step (2) resulting material is placed in progress first segment inert atmosphere sintering in tube furnace, inert atmosphere is argon
Gas, the temperature increasing schedule of heat treatment are 10 DEG C/min, and holding temperature is 400 DEG C, and soaking time is 20h, obtains one-stage sintering product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is the mixed gas of hydrogen and argon gas,
The temperature increasing schedule of heat treatment is 20 DEG C/min, and holding temperature is 700 DEG C, and soaking time is 10h, is naturally cooled to after the completion of sintering
Product is passed through Mechanical Crushing and vibration separation, obtains silicon based composite material by room temperature.
4 gained silicon based composite material of comparative example is prepared into electrode, assembled battery and test by identical method in embodiment 1
Performance.
Fig. 2 is Si/GC/SiO of the present inventionxThe structural schematic diagram of composite material, for the nano-silicon for aoxidizing sub- silicon cladding
With the knitting wool spherical structure of graphitized carbon fibre pipe.Fig. 3 is Si/GC/SiO prepared by embodiment 4xThe XRD diagram of composite material, from figure
As can be seen that there are an apparent broad peaks within the scope of 2 θ=10~40 ° for gained sample, correspond to the amorphous feature of SiOx,
Nearby there is the crystal face characteristic peak an of Si (111), (220), (311) in 2 θ=28.6 °, 47.6 °, 56.2 °.Fig. 4 is real
Apply the Si/GC/SiO of the preparation of example 4xThe transmission electron microscope picture (TEM) of composite material, as can be seen from Fig., nano-silicon, graphitization carbon fiber
Dimension pipe, the sub- silicon of oxidation are compounded to form the Si/GC/SiOxComposite material.
The test that Examples 1 to 6 and 1~4 gained silicon based composite material of comparative example are carried out to lithium half-cell, as a result such as table 1
It is shown, by electrochemical property test result it is found that Examples 1 to 6 all has good comprehensive electrification in lithium ion half-cell
Learn performance.
The electrochemical property test result of 1~4 gained silicon based composite material of 1 Examples 1 to 6 of table and comparative example
Due to being added without heavy metallic salt in comparative example 1, so that the high molecular polymer PP plastics being added can not form line
Shape fiber tubular structure, also, during heat treatment, do not have graphitization characteristic by the carbon of PP plastics carbonization preparation, it is conductive
Property is poor, and then chemical property is poor.
Due to being added without montmorillonite in comparative example 2, PP plastic melt can not be inhibited to solidify in material preparation process
Agglomeration in journey, can not realize the uniform cladding for aoxidizing sub- silicon using montmorillonite as silicon source, thus chemical property compared with
Difference.
Due to being sintered without two-part in comparative example 3, so that carbonization and carbon thermal reduction effect are poor, it can neither be fine
PP plastics are carbonized, and cannot be by reducing silica, therefore chemical property is poor.
Parameter collocation in comparative example 4 due to preparation is undesirable, and selected parameter is not in preferred scope, so that prepared by material
During cannot control the structure and pattern of material well, therefore chemical property is poor.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof
It changes and also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium-ion-power cell silicon based composite material characterized by comprising
Using nano-silicon, plastics and montmorillonite as raw material, heavy metallic salt is added as catalyst, is being melted after the raw material is mixed
Under the conditions of carry out extrusion granulation, obtain nano-silicon/plastic/montmorillonite composite material；
Nonionic surfactant and cationic surfactant are added in hydrochloric acid solution, mixed solution is obtained, by nanometer
Silicon/plastic/montmorillonite composite material is added in mixed solution, is carried out solgel reaction, is obtained nano-silicon/plastics/dioxy
SiClx composite material；
Nano-silicon/plastics/silicon dioxide composite material is subjected to carbon thermal reduction, it is multiple to obtain nano-silicon/graphitized carbon/oxidation Asia silicon
Condensation material, i.e., the described lithium-ion-power cell silicon based composite material.
2. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1, which is characterized in that described
Nano-silicon, plastics and the mass ratio of montmorillonite are (1~5): (20~40): (2~10).
3. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1 or claim 2, which is characterized in that
The partial size of the nano-silicon is 100~500nm.
4. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1 or claim 2, which is characterized in that
The heavy metallic salt is one of nickel salt, cobalt salt, molysite, manganese salt or a variety of, the additive amount of heavy metallic salt be raw material 1~
5wt%.
5. the preparation method of lithium-ion-power cell silicon based composite material according to claim 4, which is characterized in that described
Nickel salt is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of；The cobalt salt is cobalt nitrate, cobalt acetate, sulfuric acid
One of cobalt, cobalt chloride are a variety of；The molysite is one of ferric nitrate, ferric acetate, ferric sulfate, iron chloride or a variety of；
The manganese salt is one of manganese nitrate, manganese acetate, manganese sulfate, manganese chloride or a variety of.
6. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1 or claim 2, which is characterized in that
The nonionic surfactant be one of Triton X2100, OP-10, TX-10, NP-8.6 or a variety of, it is described it is non-from
The additive amount of sub- surfactant is 5~10wt% of nano-silicon/plastic/montmorillonite composite material；The cationic surface is living
Property agent be cetyl trimethyl season ammonium bromide, octadecyl dimethyl benzyl season ammonium chloride, tri alkyl ammomium chloride, trialkyl first
One of ammonium chloride is a variety of, and the additive amount of the cationic surfactant is nano-silicon/plastic/montmorillonite composite wood
15~20wt% of material.
7. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1 or claim 2, which is characterized in that
The concentration of hydrochloric acid is 1~5mol/L, and hydrochloric acid and nano-silicon/plastic/montmorillonite composite material molar ratio are (1~10): 1.
8. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1 or claim 2, which is characterized in that
The plastics are one of polypropylene, polyethylene, polystyrene or a variety of.
9. the preparation method of lithium-ion-power cell silicon based composite material according to claim 1, which is characterized in that described
The preparation method of lithium-ion-power cell silicon based composite material, comprising the following steps:
(1) after mixing by nano-silicon, plastics, heavy metallic salt and montmorillonite, it is placed in double screw extruder, control melting item
Part carries out extruding pelletization under setting screw speed and processing temperature, is cooled to room temperature taking-up, and it is de- to obtain nano-silicon/plastics/illiteracy
Soil composite material；
(2) nonionic surfactant of predetermined amount and cationic surfactant are dissolved in hydrochloric acid solution, until surface-active
Agent all dissolves and after solution change clarification, is added with stirring nano-silicon/plastic/montmorillonite composite material obtained by step (1), stirring
0.5~2h, at room temperature, still aging 10~20h are then centrifuged for, and are washed, dry, obtain nano-silicon/plastics/dioxy
SiClx composite material；
(3) nano-silicon/plastics/silicon dioxide composite material obtained by step (2) is placed in progress first segment indifferent gas in tube furnace
Atmosphere sintering, inert atmosphere are selected from the mixed gas of one or more of helium, argon gas, neon, nitrogen, the heating system of heat treatment
Degree is 1~10 DEG C/min, and holding temperature is 500~800 DEG C, and soaking time is 2~12h, obtains one-stage sintering product；
One-stage sintering product is subjected to the sintering of second segment reducing atmosphere, reducing atmosphere is selected from hydrogen and helium, argon gas, neon, nitrogen
The mixed gas of one or more of gas, the temperature increasing schedule of heat treatment are 5~20 DEG C/min, and holding temperature is 900~1500
DEG C, soaking time is 2~12h, and cooled to room temperature after the completion of sintering obtains the lithium by product by broken and classification
Ion battery silicon based composite material.
10. it is a kind of according to claim 1~any one of 9 described in nano-silicon/graphitized carbon/oxidation for being prepared of preparation method
Sub- silicon composite, which is characterized in that the sub- silicon of the oxidation is clad, graphitized carbon and nano-silicon as matrix, described to receive
Rice silicon/graphitized carbon/oxidation Asia silicon composite forms core-shell structure, and the partial size of the composite material is 10~30um, nano-silicon
Mass ratio with graphitized carbon is 1:(1~10), the content for aoxidizing sub- silicon is nano-silicon/graphitized carbon/oxidation Asia silicon composite wood
2~5wt% of material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910175785.9A CN109755546B (en) | 2019-03-08 | 2019-03-08 | Preparation method of silicon-based composite material for lithium ion power battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910175785.9A CN109755546B (en) | 2019-03-08 | 2019-03-08 | Preparation method of silicon-based composite material for lithium ion power battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109755546A true CN109755546A (en) | 2019-05-14 |
| CN109755546B CN109755546B (en) | 2020-07-14 |
Family
ID=66408314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910175785.9A Active CN109755546B (en) | 2019-03-08 | 2019-03-08 | Preparation method of silicon-based composite material for lithium ion power battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109755546B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265653A (en) * | 2019-08-17 | 2019-09-20 | 潍坊科技学院 | A kind of preparation method of battery cathode stratiform silicon carbon material |
| CN110752351A (en) * | 2019-09-30 | 2020-02-04 | 金圣杰 | Method for preparing electrode plate of battery and battery by using recycled material |
| CN112028065A (en) * | 2020-08-25 | 2020-12-04 | 湖南宸宇富基新能源科技有限公司 | SiOx-SiC-C/G silicon-carbon composite material and preparation and application thereof |
| CN112259738A (en) * | 2020-10-27 | 2021-01-22 | 成都新柯力化工科技有限公司 | Method for continuously preparing lithium battery silicon-carbon negative electrode material at low temperature |
| CN115036592A (en) * | 2022-06-21 | 2022-09-09 | 中国地质大学（武汉） | Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120895A (en) * | 2005-02-02 | 2011-07-13 | 大塚化学株式会社 | Carbon nanotube-loaded inorganic particle |
| CN102867944A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Mesoporous carbon/silicon composite anode material and preparation method thereof |
| KR20140082571A (en) * | 2012-12-24 | 2014-07-02 | 이화여자대학교 산학협력단 | Silicon nanosheet and preparing method of the same |
| WO2017146237A1 (en) * | 2016-02-25 | 2017-08-31 | 旭化成株式会社 | Nonaqueous electrolyte battery inorganic particles and nonaqueous electrolyte battery |
| US20170331092A1 (en) * | 2016-05-13 | 2017-11-16 | Quantumscape Corporation | Solid electrolyte separator bonding agent |
| CN108140876A (en) * | 2015-10-26 | 2018-06-08 | 株式会社日立制作所 | The manufacturing method of lithium rechargeable battery and lithium rechargeable battery |
| CN108365177A (en) * | 2018-02-28 | 2018-08-03 | 北京鼎能开源电池科技股份有限公司 | A kind of high safety type ternary battery cathode sheet and preparation method thereof |
| CN108358206A (en) * | 2018-03-02 | 2018-08-03 | 中南大学 | A kind of three-dimensional crosslinking structure silicon nano material and its preparation method and application |
| CN109346716A (en) * | 2018-11-23 | 2019-02-15 | 内蒙古科技大学 | A kind of method that non-wood papermaking raw material alkali process waste liquid prepares C/SiOx composite lithium ion battery negative electrode material |
-
2019
- 2019-03-08 CN CN201910175785.9A patent/CN109755546B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120895A (en) * | 2005-02-02 | 2011-07-13 | 大塚化学株式会社 | Carbon nanotube-loaded inorganic particle |
| CN102867944A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Mesoporous carbon/silicon composite anode material and preparation method thereof |
| KR20140082571A (en) * | 2012-12-24 | 2014-07-02 | 이화여자대학교 산학협력단 | Silicon nanosheet and preparing method of the same |
| CN108140876A (en) * | 2015-10-26 | 2018-06-08 | 株式会社日立制作所 | The manufacturing method of lithium rechargeable battery and lithium rechargeable battery |
| WO2017146237A1 (en) * | 2016-02-25 | 2017-08-31 | 旭化成株式会社 | Nonaqueous electrolyte battery inorganic particles and nonaqueous electrolyte battery |
| US20170331092A1 (en) * | 2016-05-13 | 2017-11-16 | Quantumscape Corporation | Solid electrolyte separator bonding agent |
| CN108365177A (en) * | 2018-02-28 | 2018-08-03 | 北京鼎能开源电池科技股份有限公司 | A kind of high safety type ternary battery cathode sheet and preparation method thereof |
| CN108358206A (en) * | 2018-03-02 | 2018-08-03 | 中南大学 | A kind of three-dimensional crosslinking structure silicon nano material and its preparation method and application |
| CN109346716A (en) * | 2018-11-23 | 2019-02-15 | 内蒙古科技大学 | A kind of method that non-wood papermaking raw material alkali process waste liquid prepares C/SiOx composite lithium ion battery negative electrode material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110265653A (en) * | 2019-08-17 | 2019-09-20 | 潍坊科技学院 | A kind of preparation method of battery cathode stratiform silicon carbon material |
| CN110265653B (en) * | 2019-08-17 | 2019-12-10 | 潍坊科技学院 | Preparation method of layered silicon-carbon material for battery cathode |
| CN110752351A (en) * | 2019-09-30 | 2020-02-04 | 金圣杰 | Method for preparing electrode plate of battery and battery by using recycled material |
| CN112028065A (en) * | 2020-08-25 | 2020-12-04 | 湖南宸宇富基新能源科技有限公司 | SiOx-SiC-C/G silicon-carbon composite material and preparation and application thereof |
| CN112259738A (en) * | 2020-10-27 | 2021-01-22 | 成都新柯力化工科技有限公司 | Method for continuously preparing lithium battery silicon-carbon negative electrode material at low temperature |
| CN115036592A (en) * | 2022-06-21 | 2022-09-09 | 中国地质大学（武汉） | Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof |
| CN115036592B (en) * | 2022-06-21 | 2023-08-29 | 中国地质大学（武汉） | Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109755546B (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109755546A (en) | A kind of preparation method of lithium-ion-power cell silicon based composite material | |
| CN103199254B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| KR101685776B1 (en) | Nanosiliconcarbon composite material and preparation method therefor | |
| CN103066243B (en) | Coke powder-based cathode material of lithium ion power battery and preparation method thereof | |
| CN104638252B (en) | Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery | |
| CN109755482B (en) | Silicon/carbon composite material and preparation method thereof | |
| CN108649198B (en) | Synthesis method of cobalt-embedded nitrogen and sulfur co-doped carbon nanomaterial | |
| CN106784819B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN103236534B (en) | A kind of preparation method of lithium ion battery silicon oxide/carbon composite negative pole material | |
| CN112750987B (en) | Lithium metal negative electrode preparation method based on lithium-philic three-dimensional carbon-based current collector | |
| CN110299516A (en) | The preparation method of carbon nano pipe array load lithium titanate flexible electrode material | |
| CN105355875B (en) | A kind of tungsten oxide nano wound composite, preparation method and application | |
| CN107634199A (en) | A kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery | |
| CN104303339B (en) | Anode material of secondary cell and preparation method thereof | |
| CN105390687A (en) | High-performance three-dimensional carbon nanotube composite negative electrode material, preparation method therefor and application thereof | |
| CN105428611A (en) | High-performance porous-hollow composite anode material and preparation method and application thereof | |
| CN107293704B (en) | Carbon coating lithium sulfide nanocrystal composite, preparation method and application | |
| CN108735983A (en) | A kind of metal nanoparticle is carried on graphene hydrogel composite material and its preparation method and application | |
| CN106784743A (en) | A kind of low thermal expansion porous silicon/graphite combination electrode material and preparation method thereof | |
| CN109411713A (en) | The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery | |
| CN109616634A (en) | One kind being based on hetero atom chalcogen solid solution TexSeySzPositive electrode material of lithium secondary cell and preparation method | |
| CN106058179A (en) | Preparation method of carbon nanotube/silica/carbon composite cathode material | |
| Qiao et al. | One-step in situ encapsulation of Ge nanoparticles into porous carbon network with enhanced electron/ion conductivity for lithium storage | |
| CN109817925A (en) | Lithium ion secondary battery Si oxide composite negative pole material and preparation method | |
| CN102867945B (en) | Preparation method of graphite negative electrode material containing hollow carbon nanostructure for lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |