CN109755515A - A kind of lithium ion battery silicon/anode composite and preparation method thereof - Google Patents
A kind of lithium ion battery silicon/anode composite and preparation method thereof Download PDFInfo
- Publication number
- CN109755515A CN109755515A CN201811616291.1A CN201811616291A CN109755515A CN 109755515 A CN109755515 A CN 109755515A CN 201811616291 A CN201811616291 A CN 201811616291A CN 109755515 A CN109755515 A CN 109755515A
- Authority
- CN
- China
- Prior art keywords
- silicon
- lithium ion
- ion battery
- anode composite
- battery silicon
- 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
Abstract
The invention discloses a kind of lithium ion battery silicon/anode composites, have core-shell structure, and kernel is the silicon particle of porous structure, and shell is the tortuous carbon nano tube bundle with a large amount of gaps, and the two interface is attached with metal silicide.In the present invention, the porosity of silicon particle significantly alleviates volume expansion of the silicon in charge and discharge process, improves diffusion of the lithium ion inside silicon；The high conductivity of carbon nano tube bundle overcomes the low disadvantage of silicon electron conduction itself, while as outer buffer layer flexible, further alleviating the volume expansion of silicon；Metal silicide constructs electron propagation ducts as tight junctions between silicon and carbon nanotube, and can prevent carbon nanotube from falling off in charge and discharge process.New structural silicon/anode composite provided by the invention has many advantages, such as that high specific capacity, good cycle and high rate performance are excellent in lithium ion battery applications, and preparation cost is low, and method is simple, industrialized production easy to accomplish.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of new structural lithium ion battery
Silicon/anode composite and preparation method thereof.
Background technique
Lithium ion battery is high with energy density, operating voltage is high, charging rate is fast, has extended cycle life, is environmental-friendly, peace
Full stable performance advantage is current green energy-storing power supply most with prospects, is widely used in mobile electronic device, electronic
Automobile and electronic field.But with electronic apparatus miniaturization, energetic, the growth requirement of portability and New energy electric vapour
The popularization and application of vehicle require all technical of lithium ion battery higher and higher.
Currently used lithium ion battery negative material is graphite, and theoretical specific capacity is only 372mAhg-1, cannot
Meet current lithium ion battery to height ratio capacity and high-power application requirement, develops novel high-performance negative electrode material and have become when business
It is anxious.The theoretical specific capacity of silicium cathode material is about 10 times of graphite type material, up to 3580mAh g-1, it is to be currently known to use
In the highest material of lithium cell negative pole theoretical specific capacity, and it is resourceful, cheap, it is to substitute the ideal of graphite cathode material to wait
One of material selection, but such material faces following problems in actual application: and 1) silicon can be sent out during cycle charge-discharge
Raw violent volume change (volume expansion reaches 300-400% after alloying lithium), serious volume change causes inner tensions, thus
Make electrode structure avalanche, circulating battery stability sharply declines；2) lithium diffusion coefficient in silicon materials is small；3) silicon materials electronics is led
It is electrically poor.The above problem hinders practical application of the silicon materials in lithium ion battery.
For the disadvantage for overcoming volume expansion and lithium in silicon diffusion coefficient of the silicon materials in charging small, existing technology
Solution, which is concentrated mainly on, develops porous silicon materials, including building open bore structural metal (such as Cu, Ni, Cu Al
Fe) and the silicon of carbon foam skeleton adulteration, non-filling clad (such as conductive metal, carbon, TiO2, SiO x ) cladding silicon, tool
Have gap or hole configurations nano-silicon (nano line cluster, hollow sphere, pomegranate shape, tubulose or eggshell structure nano silicon material) etc.
[1-3].But the building of silicon materials central hole structure passes through acid or alkaline etching inorganic template agent (SiO at present or mainly x , NiO,
CaCO3And Mg, Fe alloy) and thermal decomposition organic formwork agent (polymethyl methacrylate (PMMA), polyacrylonitrile (PAN) and each
Kind surfactant etc.) Lai Shixian [4-5].But in these traditional pore forming methods, the use of template not only increases preparation
Cost, and strong corrosive concentrated acid or concentrated base (HF or NaOH) is needed to handle, pollute environment.Therefore, using the preparation of no template
It is quite important that the flourishing cellular structure of method building synthesizes commercialization porous silicon-base composite material to green economy.In addition, at present
The article of lithium ion battery silicon cathode material is prepared as raw material about perlite and patent is also rarely reported, it is precious at this stage
Zhu Yan is still concentrated mainly on the application fields such as building heat preservation and industrial heat preservation.The application field for expanding in-depth perlite material, makes
Its silicium cathode material for becoming high-performance and high performance-price ratio, applies in new energy field of lithium ion battery, is expected to generate biggish
Social benefit and economic benefit.
In addition, carbon coating silicon materials are the effective measures for overcoming silicon electrode electron conduction difference, wherein carbon coating layer is filled out
Two kinds of forms [6-7] of filling property and non-filling.Wherein the carbon coating layer of fillibility can be improved electron conduction, but carbon coating
The elasticity or ductility of layer are insufficient, and the bring inner tensions in charge and discharge process cannot be effectively reduced from silicon materials, hold
Easily cause electrode structure avalanche, cycle life decline；Rather than the carbon coating layer of fillibility is due to the presence of internal voids structure, though
A large amount of gap structures that the volume expansion of silicon can so be effectively relieved, but be present between silicon and carbon also correspondingly reduce the two
Between contact area, reduce its electrons/ions electric conductivity.
Therefore, the silicon/carbon that can alleviate silicon volume expansion and stronger ion/electron conduction is constructed
Anode material structure is just able to achieve the height ratio capacity of lithium ion battery, the application requirement of high rate capability and high stability.
Summary of the invention
In order to overcome volume expansion of the silicon materials in charge and discharge process, lithium ion spread inside silicon materials it is slow and
Three big main problems of the electron conduction difference of silicon, improve the specific discharge capacity of silicon based anode material, charge and discharge cycles stability,
And high rate performance, the present invention provides a kind of lithium ion battery silicon/anode composites and preparation method thereof.
The object of the present invention is achieved like this:
A kind of lithium ion battery silicon/anode composite, it is characterised in that: the composite material has core-shell structure, and kernel is
Porous silicon particle, shell is the tortuous carbon nano tube bundle winding layer with a large amount of gap structures, and the two passes through metal silication
Object carries out riveted connection；Wherein, porous silicon particle is by being prepared by raw material using perlite；
In above-mentioned lithium ion battery silicon/anode composite, metal silicide is in nickle silicide, cobalt silicide and iron suicide
Any one.
In above-mentioned lithium ion battery silicon/anode composite, the average particle size particle size of porous silicon is at 5~50 μm
Between, inside bore dimension is between 400~1000 nm, and silicon wall thickness is between 50~200 nm；
In above-mentioned lithium ion battery silicon/anode composite, between 5~15 μm, caliber exists length of carbon nanotube
Between 50~300 nm, carbon wall thickness is 2~20 nm.
In above-mentioned lithium ion battery silicon anode material, by mass percentage, porous silica material accounts for gross mass
30~60%, carbon nano-tube material and metal silicide account for the 40~70% of gross mass.
In above-mentioned lithium ion battery silicon/anode composite, the porosity of silicon particle significantly alleviates silicon in charge and discharge
Volume expansion in electric process improves diffusion of the lithium ion inside silicon；The high conductivity of carbon nano tube bundle, overcomes
The low disadvantage of silicon electron conduction itself, while as flexible exterior buffer layer, further alleviate the volume expansion of silicon；Metal
Silicide constructs electron propagation ducts as tight junctions between silicon and carbon nanotube, and can prevent carbon nanotube
It falls off in charge and discharge process.New structural silicon/anode composite provided by the invention has in lithium ion battery applications
Have the advantages that high specific capacity, good cycle and high rate performance are excellent.
Lithium ion battery silicon/anode composite preparation method, includes the following steps:
1) 48 h of ball milling is carried out by raw material of perlite；
2) will treated that material preheated through step 1), fast heating at high temperature and rapid cooling, and after being carried out using acid solution
Processing obtains porous silica silicon materials；
3) will be through step 2 treated material carries out under high temperature inert atmosphere metallothermic reduction processing, and acid solution is utilized to carry out
Post-processing obtains porous silica material；
4) it will be uniformly mixed through step 3) treated material with metal acetate salt (or metal oxalate), hydrocarbon, and
It is roasted under high temperature inert atmosphere, obtains lithium ion battery silicon/anode composite.
In above-mentioned preparation method, step 2 is comprised the following steps: first 200oC~400o20 are preheated in C
~30 min, then 1000oC~1200o2~20 s are heated in the high temperature of C, finally quickly by material from high temperature
20 are transferred under environmentoC~35oCooling treatment is carried out at a temperature of C, then using 3~5 M hydrochloric acid 60oC~ 100o24 h are handled under C, obtain porous silica silicon materials.
In above-mentioned preparation method, step 3) is comprised the following steps；The material that step 2 obtains is mixed with magnesium powder
It closes, 650oC~750oMagnesiothermic reduction reaction is carried out under the high temperature and Ar atmosphere of C, then using at 0.5~2 M hydrochloric acid
4 h are managed, porous silica material is obtained.
In above-mentioned preparation method, step 4) is comprised the following steps: the material and metal acetate salt that step 3) is obtained
(or metal oxalate), hydrocarbon etc. are uniformly mixed, 650oC~750oThe high temperature and Ar or N of C2It is carried out under atmosphere
Roasting obtains lithium ion battery silicon/anode composite.
Further, the metal acetate salt in step 4) or metal oxalate are nickel acetate, cobalt acetate or ferrous oxalate；Carbon
Hydrogen compound is melamine, urea or dicyandiamide.
Further, the metal acetate salt in step 4) is nickel acetate；Hydrocarbon is melamine.
Positive beneficial effect: silicon/anode composite structure novel prepared by the present invention has core-shell structure, interior
Core is porous silicon particle, and silicon materials pore volume is 4~6 times of silicon wall product, can be realized self-control buffering silicon in charge and discharge
Volume expansion in electric process improves the charge and discharge cycles stability of silicon materials；The present invention is by opening using perlite as raw material
The silicon-based anode material of lithium-ion battery of sending shows high performance-price ratio application advantage.In addition, entire technical process is not required to
Expensive silicon precursor, template are used, preparation cost is low, simple process, silicon-based anode material easy to accomplish
Industrialized production, can satisfy lithium ion battery scale application requirement.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of porous silica material made from the embodiment of the present invention 1；
Fig. 2 is silicon/anode composite scanning electron microscope (SEM) photograph made from the embodiment of the present invention 1；
Fig. 3 is silicon/anode composite charge-discharge property figure made from the embodiment of the present invention 1；
Fig. 4 is 500 charge and discharge cycles stability of silicon/anode composite made from the embodiment of the present invention 1；
Fig. 5 is silicon/anode composite high rate performance made from the embodiment of the present invention 1.
Specific embodiment
Combined with specific embodiments below, the present invention is described further:
Embodiment 1
(1) using perlite as raw material, perlite is placed in the agate jar of 100ml, and the agate of diameter 20mm is added
The agate ball 10g of the agate ball 40g of ball 50g, diameter 10mm, diameter 5mm.Wherein, the mass ratio of agate ball and perlite is 20:
1, ball milling speed is 450 rpm, ball milling 48h obtains micron-sized perlite particle.
(2) 300oC preheats 25 min, then 1100oC heats 10s, finally quickly by material from lower turn of hot environment
Move to 25oC's or so is cooled down at room temperature, then with 4M hydrochloric acid 80oIt is handled under C for 24 hours, it is cleaned, it filters, it is dry, it obtains
Obtain porous earth silicon material.
(3) 10g porous silica is mixed with 10g magnesium powder, 700oMagnesiothermic reduction is carried out under C and Ar atmosphere
Reaction, then through 1 M hydrochloric acid in 80oC handles 4h, obtains porous silica material.
(4) by 3g porous silica material and 3.2g nickel acetate, 7.5g melamine is uniformly mixed, and 700oC and Ar atmosphere
Under roasted, obtain silicon/anode composite of nickle silicide connecting carbon nanotube and porous silicon.In the composite, more
Hole silicon materials account for the 45.1 of composite material gross masswt%。
By silicon/anode composite: carbon black: polyacrylic acid is mixed according to mass ratio for 8:1:1, with N-methyl pyrrolidines
Ketone is prepared into slurry and coats to copper foil surface as molten Ji, and for 24 hours, working electrode piece is made in drying at 120 DEG C.To electrode
For lithium piece, electrolyte is 1.0 M LiPF6/ EC(ethylene carbonate): DMC(dimethyl carbonate)=1:1 (V/V)/10wt%'s
FEC(fluorinated ethylene carbonate).Button cell (CR2032) is assembled into high-purity argon gas glove box.It is surveyed using Land battery
It tries instrument and carries out constant current charge-discharge test, study silicon/anode composite charging and discharging capacity and cycle performance.Voltage is surveyed
Examination range: 0.01-2.0 V (vs Li/Li+)。
As can be seen from Figure 1, using perlite as raw material, the porous silica material prepared by the method for the invention shows abundant big
Pore structure, aperture size are distributed in 600-900 nm, and silicon wall thickness is 100- 150nm, and mesoporous-wall volume ratio is about 6, is
Nearly twice (silicon volume expansion after embedding lithium is about 300-400%) of the silicon materials volume of embedding lithium, can overcome silicon in charge and discharge
Volume expansion in journey improves the charge and discharge cycles stability of silicon materials.
From figure 2, it is seen that porous silicon particle of silicon/anode composite pattern for carbon nanotube winding, and carbon pipe
It is attached with porous silicon by the nickle silicide generated in interface.This novel structure can guarantee silicon/anode composite
With good electron conduction, Ionic diffusion and structural stability, so as to be showed in lithium ion battery applications
Excellent charge-discharge performance, high rate performance and cyclical stability out.
As can be seen from Figure 3, with 358mA/g (0.1 C) carry out charge-discharge test, silicon/anode composite discharge for the first time with
Charge specific capacity is respectively 2418 mAh g-1With 1956 mAh g-1, coulombic efficiency 80.9%.In 100 charge and discharge cycles
Afterwards, average coulombic efficiency has reached 99.7%.
As can be seen from Figure 4, silicon/anode composite is put at 358 mA/g (0.1 C) after charge and discharge cycles 500 times
Electric specific capacity is still up to 1547mAhg-1, capacity retention ratio shows high charge and discharge cycles stability 99.5%.
As can be seen from Figure 5, with 716 (0.2 C), 1790 (0.5 C), 3580(1 C) and 7160 (2 C) mA g-1It is filled
After discharging 100 weeks, silicon/anode composite specific discharge capacity is respectively 1365,1176,974 and 778 mAh g-1, it is in
Reveal excellent charge-discharge magnification performance.
Embodiment 2
Step (1-3) is identical as the preparation process of embodiment 1, in step (4), by 3 g porous silica materials and 3.5 g acetic acid
Cobalt, 7.6 g dicyandiamides are uniformly mixed, and 700oRoasted under C and Ar atmosphere, obtain cobalt silicide connecting carbon nanotube and
Silicon/anode composite of porous silicon.In the composite, porous silica material accounts for the 43.2 of composite material gross masswt%.It should
The chemical property of composite material is as shown in table 1.
Embodiment 3
Step (1-3) is identical as the preparation process of embodiment 1, in step (4), 3 g porous silica materials and 3.2g oxalic acid are sub-
Iron, 7.6 g urea are uniformly mixed, and 700oIt is roasted under C and Ar atmosphere, obtains iron suicide connecting carbon nanotube and more
Silicon/anode composite of hole silicon.In the composite, porous silica material accounts for the 40.6 of composite material gross masswt%.This is multiple
The chemical property of condensation material is as shown in table 1.
Silicon/anode composite charge-discharge performance in 1. embodiment of table
As can be seen from the above table, silicon/anode composite specific discharge capacity with higher and excellent in the present invention
Cyclical stability, capacity retention ratio solves the poor circulation of existing silicium cathode material 91% or more after recycling 500 times
Problem, the further satisfaction application demand of high-performance and high stability lithium ion battery.
In aforementioned present invention preparation method, using the perlite of rich reserves as raw material, first passes around ball milling and obtain micron
The perlite particle of rank is constructed at porous structure and rapid cooling by being further heat-treated volatile material internal crystallization water
Fixed hole shape is managed, the expanded perlite of porous structure is obtained, the titanium dioxide of porous structure is then obtained after the sour processing of progress
Silicon materials.Subsequent porous silica is handled through metallothermic reduction and acid, obtains the silicon materials of porous structure.Finally, using gold
Belong to acetate (or metal oxalate), hydrocarbon be presoma, using transition metal in high-temperature calcination process (Ni, Co,
Fe) terminal catalytic carbon nano tube growth mechanism generates the carbon nano-tube material of top insertion transition metal.And in carbon nanotube
The transition metal (Ni, Co, Fe) of insertion further can generate metal silicide by alloying reaction with porous silicon particle, from
And securely connect carbon nanotube clad with porous silicon particle, finally prepare high performance lithium ion battery silicon/carbon
Anode material.The preparation method is low in cost, and preparation process is simple, economic and environment-friendly, is very suitable to large-scale industry metaplasia
It produces, is expected to accelerate commercial applications of the silicon based anode material in lithium ion battery.
Following methods characterization can be used in obtained silicon/anode composite: by obtained silicon/Carbon anode composite wood
Material, carbon black or graphite powder, polyacrylic acid are gathered inclined tetrafluoroethene or acid methyl cellulose and are mixed with the ratio of mass ratio 8:1:1
It closes slurrying and is applied to copper foil surface, dried at 120 DEG C, punching is prepared into negative electrode tab, the use of lithium piece is to electrode, in high-purity argon
Button cell is assembled into gas glove box.Above-mentioned prepared silicon/anode composite is applied to show in lithium ion battery
Higher specific discharge capacity out, good charge-discharge performance and high rate performance.
Moreover, the present invention is presented by the silicon-based anode material of lithium-ion battery using perlite as raw material, developed
High performance-price ratio application advantage out.In addition, entire technical process is not needed using expensive silicon precursor, template, preparation
At low cost, simple process, the industrialized production of silicon-based anode material easy to accomplish can satisfy the scale of lithium ion battery
Change application requirement.
Silicon prepared by the present invention/anode composite structure novel, has core-shell structure, and kernel is porous silicon
Grain, and silicon materials pore volume is 4~6 times of silicon wall product, can be realized body of the self-control buffering silicon in charge and discharge process
Product expansion, improves the charge and discharge cycles stability of silicon materials；
The porosity of silicon particle significantly improves diffusion of the lithium ion inside silicon in the present invention, and it is accessible to increase material
Specific surface area active and stock utilization are conducive to improve silicon/anode composite storage lithium specific capacity and high rate performance.
Carbon nano tube bundle in the present invention forms spongy buffering on silicon materials surface as external flexible winding layer
The flourishing gap structure that layer and carbon nano tube bundle are formed, has further buffered the volume expansion of silicon.Meanwhile carbon nanotube
High conductivity overcomes the low disadvantage of silicon semiconductor material electron conduction, enhances silicon/anode composite electronics biography
Movement Capabilities.
Secured tie point of the metal silicide as carbon nanotube and silicon particle in the present invention, silicon and carbon nanotube it
Between constructed quick electron propagation ducts, and can prevent carbon nanotube in charge and discharge process by silicon volume change institute
It is caused to fall off, further improve silicon/anode composite electron transport ability and cyclical stability.
Preparation method of the invention is not needed using expensive silicon precursor and pore structure template etc., but straight
It connects using the preparation method without template, uses the perlite of rich reserves for raw material, by carrying out physical chemistry to perlite
Deep processing processing, realizes the high added value development and utilization of perlite material, and develops the lithium of high-performance and high performance-price ratio
Ion battery silicon/anode composite shows superior specific discharge capacity compared to traditional graphite cathode material
With high rate performance, there is biggish Social benefit and economic benefit.In addition, the preparation method is low in cost, simple process is easy
Realize large-scale industrial production.
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 by upper
Embodiment is stated the present invention is described in detail, however, those skilled in the art should understand that, can in form and
Various changes are made in details to it, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of lithium ion battery silicon/anode composite, it is characterised in that: the composite material has core-shell structure, kernel
For porous silicon particle, shell is the tortuous carbon nano tube bundle winding layer with a large amount of gap structures, and the two passes through metallic silicon
Compound carries out riveted connection；Wherein, porous silicon particle is by being prepared by raw material using perlite.
2. a kind of lithium ion battery silicon/anode composite according to claim 1, it is characterised in that: above-mentioned lithium
In ion battery silicon/anode composite, metal silicide is any one in nickle silicide, cobalt silicide and iron suicide.
3. a kind of lithium ion battery silicon/anode composite according to claim 1, it is characterised in that: above-mentioned
In lithium ion battery silicon/anode composite, the average particle size particle size of porous silicon is between 5~50 μm, inside bore dimension
Between 400~1000 nm, silicon wall thickness is between 50~200 nm.
4. a kind of lithium ion battery silicon/anode composite according to claim 1, it is characterised in that: above-mentioned
In lithium ion battery silicon/anode composite, length of carbon nanotube is between 5~15 μm, and caliber is in 50~300 nm
Between, carbon wall thickness is 2~20 nm.
5. a kind of lithium ion battery silicon/anode composite according to claim 1, it is characterised in that: above-mentioned
In lithium ion battery silicon anode material, by mass percentage, porous silica material accounts for the 30~60% of gross mass, carbon nanotube
Material and metal silicide account for the 40~70% of gross mass.
6. a kind of lithium ion battery silicon/anode composite according to claim 1, it is characterised in that: in above-mentioned lithium
In ion battery silicon/anode composite, it is swollen that the porosity of silicon particle significantly alleviates volume of the silicon in charge and discharge process
It is swollen, improve diffusion of the lithium ion inside silicon；The high conductivity of carbon nano tube bundle overcomes silicon electron conduction itself
Low disadvantage, while as flexible exterior buffer layer, further alleviate the volume expansion of silicon；Metal silicide, which is used as, closely to be connected
Contact constructs electron propagation ducts between silicon and carbon nanotube, and can prevent carbon nanotube from falling off in charge and discharge process.
7. lithium ion battery silicon/anode composite preparation method as described in claim 1-6 Arbitrary Term, including it is as follows
Step:
1) 48 h of ball milling is carried out by raw material of perlite；
2) will treated that material preheated through step 1), fast heating at high temperature and rapid cooling, and after being carried out using acid solution
Processing obtains porous silica silicon materials；
3) will be through step 2 treated material carries out under high temperature inert atmosphere metallothermic reduction processing, and acid solution is utilized to carry out
Post-processing obtains porous silica material；
4) it will be uniformly mixed through step 3) treated material with metal acetate salt (or metal oxalate), hydrocarbon, and
It is roasted under high temperature inert atmosphere, obtains lithium ion battery silicon/anode composite.
8. the preparation method of lithium ion battery silicon/anode composite according to claim 7, it is characterised in that:
In above-mentioned preparation method, step 2 is comprised the following steps: first 200oC~400o20~30 min are preheated in C,
Then 1000oC~1200o2~20 s are heated in the high temperature of C, finally quickly shift material under hot environment
To 20oC~35oCooling treatment is carried out at a temperature of C, then using 3~5 M hydrochloric acid 60oC~ 100 oIt is handled under C
24 h obtain porous silica silicon materials.
9. the preparation method of lithium ion battery silicon/anode composite according to claim 7, it is characterised in that:
In above-mentioned preparation method, step 3) is comprised the following steps；The material that step 2 obtains is mixed with magnesium powder, 650oC
~750oMagnesiothermic reduction reaction is carried out under the high temperature and Ar atmosphere of C, then uses 0.5~2 M HCl treatment, 4 h, is obtained
Porous silica material.
10. the preparation method of lithium ion battery silicon/anode composite according to claim 7, it is characterised in that:
In above-mentioned preparation method, step 4) is comprised the following steps: material and metal acetate salt (or the metal oxalic acid that step 3) is obtained
Salt), hydrocarbon etc. be uniformly mixed, 650oC~750oThe high temperature and Ar or N of C2It is roasted under atmosphere, obtains lithium
Ion battery silicon/anode composite；Metal acetate salt or metal oxalate in step 4) are nickel acetate, cobalt acetate or grass
It is sour ferrous；Hydrocarbon is melamine, urea or dicyandiamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811616291.1A CN109755515B (en) | 2018-12-27 | 2018-12-27 | Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811616291.1A CN109755515B (en) | 2018-12-27 | 2018-12-27 | Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109755515A true CN109755515A (en) | 2019-05-14 |
| CN109755515B CN109755515B (en) | 2020-05-22 |
Family
ID=66404115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811616291.1A Active CN109755515B (en) | 2018-12-27 | 2018-12-27 | Silicon/carbon cathode composite material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109755515B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110148743A (en) * | 2019-07-05 | 2019-08-20 | 珠海冠宇电池有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof and lithium ion battery |
| CN113363437A (en) * | 2021-05-18 | 2021-09-07 | 恒大新能源技术(深圳)有限公司 | Silicon-based negative electrode material and preparation method thereof, negative plate and secondary battery |
| WO2022062321A1 (en) * | 2020-09-27 | 2022-03-31 | 溧阳天目先导电池材料科技有限公司 | Silicon-based negative electrode composite material and lithium secondary battery |
| WO2023124405A1 (en) * | 2021-12-28 | 2023-07-06 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material and preparation method therefor, and lithium ion battery |
| CN116936789A (en) * | 2023-09-18 | 2023-10-24 | 四川赛科检测技术有限公司 | Double-layer structured silicon-carbon composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013147958A2 (en) * | 2012-01-19 | 2013-10-03 | Envia Systems, Inc. | Porous silicon based anode material formed using metal reduction |
| CN104934573A (en) * | 2014-03-19 | 2015-09-23 | 苏州格瑞动力电源科技有限公司 | In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof |
| CN105489840A (en) * | 2016-01-13 | 2016-04-13 | 哈尔滨工业大学深圳研究生院 | Silicon-based anode material of lithium ion battery and preparation method of silicon-based anode material |
| CN105845911A (en) * | 2016-05-15 | 2016-08-10 | 东北电力大学 | Method for preparing porous silicon carbon nanotube composite negative electrode material of lithium ion battery by diatomite |
-
2018
- 2018-12-27 CN CN201811616291.1A patent/CN109755515B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013147958A2 (en) * | 2012-01-19 | 2013-10-03 | Envia Systems, Inc. | Porous silicon based anode material formed using metal reduction |
| CN104934573A (en) * | 2014-03-19 | 2015-09-23 | 苏州格瑞动力电源科技有限公司 | In-situ solid-phase synthesis method of silicon-graphene spheroidal composite material with multilevel structure and application thereof |
| CN105489840A (en) * | 2016-01-13 | 2016-04-13 | 哈尔滨工业大学深圳研究生院 | Silicon-based anode material of lithium ion battery and preparation method of silicon-based anode material |
| CN105845911A (en) * | 2016-05-15 | 2016-08-10 | 东北电力大学 | Method for preparing porous silicon carbon nanotube composite negative electrode material of lithium ion battery by diatomite |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110148743A (en) * | 2019-07-05 | 2019-08-20 | 珠海冠宇电池有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof and lithium ion battery |
| WO2022062321A1 (en) * | 2020-09-27 | 2022-03-31 | 溧阳天目先导电池材料科技有限公司 | Silicon-based negative electrode composite material and lithium secondary battery |
| CN113363437A (en) * | 2021-05-18 | 2021-09-07 | 恒大新能源技术(深圳)有限公司 | Silicon-based negative electrode material and preparation method thereof, negative plate and secondary battery |
| WO2023124405A1 (en) * | 2021-12-28 | 2023-07-06 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material and preparation method therefor, and lithium ion battery |
| CN116936789A (en) * | 2023-09-18 | 2023-10-24 | 四川赛科检测技术有限公司 | Double-layer structured silicon-carbon composite material and preparation method and application thereof |
| CN116936789B (en) * | 2023-09-18 | 2023-12-05 | 四川赛科检测技术有限公司 | Double-layer structured silicon-carbon composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109755515B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109755515A (en) | A kind of lithium ion battery silicon/anode composite and preparation method thereof | |
| CN106099113B (en) | A kind of core-shell structure Si-C composite material and preparation method thereof | |
| CN108598431A (en) | Grapheme foam-nickel oxide combination electrode material and preparation method thereof | |
| CN106784752B (en) | Lithium ion battery porous structure Si/Cu combination electrode and its manufacturing method | |
| CN112850690B (en) | Preparation method of graphene-loaded double-transition metal sulfide composite material and sodium storage application | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN109616331B (en) | Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof | |
| CN109742335A (en) | Lithium ion battery silicon substrate composite negative pole material and preparation method thereof and lithium ion battery | |
| CN108615886A (en) | A kind of thin wall type porous carbon ball material and its preparation and the application as anode material of lithium-ion battery | |
| CN108110228A (en) | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof | |
| CN105958037B (en) | Sodium-ion battery cathode copper sulfide/graphene composite material and preparation method | |
| CN110790322B (en) | Core-shell nickel ferrite and preparation method thereof, nickel ferrite @ C material and preparation method and application thereof | |
| CN104167540A (en) | Negative electrode active material and preparation method thereof and lithium ion battery | |
| CN110880589B (en) | Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof | |
| CN106654238A (en) | Stannic oxide/carbon/nitrogen doped graphene composite material with pore structure as well as preparation method and application thereof | |
| CN104638253A (en) | Preparation method of Si and C-RG core-shell composite material used as cathode of lithium ion battery | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN105428618A (en) | Preparation method for shell-core type carbon-coated metal sulfide nano-composite particles and application of particles | |
| CN104538585B (en) | Hollow porous micron order silicon ball, silicon based anode material and preparation method of lithium ion battery | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN110323442A (en) | A kind of carbon coating Fe3O4Composite material and preparation method and application | |
| CN107464938A (en) | A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery | |
| CN110224126B (en) | Iron-nickel sulfide nano material and preparation method and application thereof | |
| CN109148851A (en) | A kind of silicon-carbon composite cathode material and preparation method thereof of double carbon structure modifications | |
| CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof |
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 |