CN106941174A - A kind of nitrogen doped silicon charcoal composite negative pole material and preparation method thereof - Google Patents
A kind of nitrogen doped silicon charcoal composite negative pole material and preparation method thereof Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of nitrogen doped silicon charcoal composite negative pole material, including nano Si sandwich layer and the N doping layer of charcoal for being wrapped in nano Si sandwich layer periphery, the wherein mass content of silicon is (27.32 ± 0.2) %.Nitrogen doped silicon charcoal composite negative pole material of the present invention, ball-type is smooth regular, and dispersiveness preferably, is used as the active material of lithium ion battery negative material, tests its chemical property (current density：100mA/g, voltage：0.02 1.5V), as a result show, the specific capacity and cyclical stability of composite are superior to pure silicon negative pole, and the capability retention of material is higher；Preparation method of the present invention is simple, and mild condition, reaction time is short, easy to operate, nitrogen content is high.
Description
Technical field
The present invention relates to a kind of nitrogen doped silicon charcoal composite negative pole material and preparation method thereof, belong to electrochemical field.
Background technology
Lithium ion battery is because standby with the excellent chemical property such as energy density height, memory-less effect, long circulation life
It is concerned.With the fast development of high-tech product, people are more and more harsher for the requirement of lithium ion battery negative material.
As novel high-capacity negative material, the embedding de- lithium current potential of silicon is low, be very promising lithium ion battery negative material it
One [Energy＆Environmental Science, 2011,4,3243-3262], but in charge and discharge process, silicon has
Serious bulk effect, with lithium formation alloy when occur volumetric expansion (>300%), capacity rapid decay, and destroy electrode
The structure of material, so as to cause electrode efflorescence, this turns into limitation silicium cathode and realizes commercialized difficult point
[Electrochemistry Communications,2007,9,796-800].The life of Carbon Materials and the mankind are closely related,
Because conductive good, heat resistance is good, high thermal conductivity coefficient, surface chemistry inertia many advantages, such as, and be widely used as lithium from
Sub- battery electrode material, silicon is suitably combined with Carbon Materials, is conducive to improving the chemical property of material.
Recently, researcher is keen to Carbon Materials carrying out modification, and wherein N doping Carbon Materials turn into study hotspot.Nitrogen
The atomic radius of atom and being close for carbon atom, nitrogen atom doping is entered in Carbon Materials on carbon atom surface to increase and lived
Property site, and then increase negative material reversible capacity, the electric conductivity of material can also be improved.The method of N doping Carbon Materials
Have a lot, Chen etc., which thinks to be broadly divided into, to be handled the post treatment method of Carbon Materials using ammonia, ammoniacal liquor etc. and directly utilize nitrogenous material
The method for expecting to carry out high temperature pyrolysis for presoma, but the nitrogen content of material that the former obtains is relatively low, and the latter can prepare it is nitrogenous
The higher N doping Carbon Materials [ACS Nano, 2012,6,7092-7102] of amount.Lei etc. is prepared for nitrogen by nitrogen source of pyrroles and mixed
Miscellaneous composite negative pole material, improves the chemical property [Electrochimica Acta, 2016,192,22-29] of material.
The preparation of current N doping composite still suffers from following problem：
1st, reaction condition is harsher, and such as high temperature or reaction time are long, add experimental cost.
2nd, reaction needs to additionally introduce nitrogen, ammonia etc. post-processes to material, and operation is more cumbersome, and nitrogen content compared with
It is low.
The content of the invention
In order to solve drawbacks described above present in prior art, the present invention provides a kind of nitrogen doped silicon charcoal composite negative pole material
And preparation method thereof.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
A kind of nitrogen doped silicon charcoal composite negative pole material, including nano Si sandwich layer and the nitrogen for being wrapped in nano Si sandwich layer periphery
Doping layer of charcoal, the wherein mass content of silicon are (27.32 ± 0.2) %.
In order to improve the chemical property of composite, the average grain diameter of composite is 10.1 ± 0.5 μm.
In order to simplify operation, while ensureing the chemical property of resulting materials, the system of nitrogen doped silicon charcoal composite negative pole material
Preparation Method, first passes through sol-gal process in one layer of SiO of nano Si Surface coating2, obtain Si@SiO2；Then again by anti-phase outstanding
Floating polymerization, utilizes polyacrylamide coated Si@SiO2, SiO is etched using HF after high-temperature activation2, obtain nitrogen doped silicon charcoal and be combined
Negative material.
In order to further improve reaction efficiency, while ensureing the chemical property of resulting materials, used by inverse suspension polymerization
Monomer is acrylamide, and crosslinking agent is N, and N- methylene-bisacrylamides, initiator is potassium peroxydisulfate, and coagulant is N, N, N ',
N '-tetramethylethylenediamine.
In order to further improve the chemical property of composite, Si@SiO2Mass ratio with acrylamide monomer is
(0.3 ±0.1):1。
The preparation method of above-mentioned nitrogen doped silicon charcoal composite negative pole material, is carried out in accordance with the following steps successively：
1) by sol-gal process in one layer of SiO of nano Si Surface coating2, obtain Si@SiO2, wherein Si and SiO2Matter
Amount is than being 3:(5±1)；
2) by acrylamide, N,N methylene bis acrylamide and potassium peroxydisulfate at room temperature stirring and dissolving in deionized water
In, then by Si@SiO2Ultrasonic disperse is used as aqueous phase in wherein；Wherein, acrylamide, N, N- methylene-bisacrylamides,
Potassium peroxydisulfate, water, Si@SiO2Mass ratio be：5:(0.2±0.1):(0.054±0.01):(15±2):(1.5 ± 0.2),
Si@SiO2Mass ratio with acrylamide is 0.3:1；
3) by sorbester p17 stirring and dissolving in hexamethylene, 0.5 ± 0.1h is persistently stirred after dissolving, oil phase is used as；Wherein,
The mass ratio of sorbester p17 and acrylamide is (0.15 ± 0.02):1, the consumption of hexamethylene is every gram of sorbester p17 with 100 ± 5mL；
4) aqueous phase is added dropwise in oil phase, in 9000 ± 500r/min, 20 ± 5min of down cut, then in 500 ± 100r/
Min mixing speeds, the lower progress inverse suspension polymerization reaction of nitrogen protection, reaction temperature are slowly increased in 0.5h from room temperature
50-60 DEG C, heated up 0.5 ± 0.1h of follow-up continuous stirring in place, and 1mL accelerator solution is then added into reaction system, is continued
1.5 ± 0.2h is reacted, after reaction terminates, absolute ethanol washing is added into reaction system, 80 ± 5 DEG C of 8 ± 1 h of drying are obtained
Polyacrylamide coated Si@SiO2Complex microsphere, wherein accelerator solution is the N that concentration is 0.1 ± 0.01g/mL, N, N ',
N '-tetramethylethylenediamine aqueous solution, N, N, N ', the mass ratio of N '-tetramethylethylenediamine and acrylamide is 0.02: (1±
0.1)；
5) complex microsphere is activated in argon atmosphere high temperature, SiO is etched with HF after cooling2, washing to neutrality, 80 ± 5
DEG C vacuum drying 8 ± 1h obtain nitrogen doped silicon charcoal composite negative pole material.
Step 4) in washing there is no hexamethylene, sorbester p17 etc. into solution untill, in general wash 4 times.
In order to ensure the chemical property of gained composite, high-temperature activation is：Complex microsphere is warming up to 700-800
DEG C, constant temperature 2-3h heats up as 5 ± 1 DEG C/min of speed.
In order to ensure products obtained therefrom quality, step 3) in oil phase must prepare at 30 ± 5 DEG C complete.Step 4) in liter
Temperature is slowly increased to 50-60 DEG C in 0.5h for reaction temperature from 30 ± 5 DEG C.
The NM technology of the present invention is with reference to prior art.
Nitrogen doped silicon charcoal composite negative pole material of the present invention, ball-type is smooth regular, and dispersiveness preferably, is used as lithium-ion electric
The active material of pond negative material, tests its chemical property (current density：100mA/g, voltage：0.02-1.5V), as a result
Show, the specific capacity and cyclical stability of composite are superior to pure silicon negative pole, and the capability retention of material is higher；The present invention
Preparation method is simple, and mild condition, reaction time is short, easy to operate, nitrogen content is high.
Brief description of the drawings
Fig. 1 is the FT-IR figures of acrylamide, polyacrylamide and C/N-Si-800 in embodiment 1.
Fig. 2 is the SEM figures of C/N-Si-800 in embodiment 1.
Fig. 3 is constant current charge-discharge circulation and the coulombic efficiency of nano-silicon, C/N-800 and C/N-Si-800 in embodiment 1
Curve map.
Fig. 4 is the thermogravimetric curve of C/N-Si-800 in embodiment 1.
Fig. 5 is the XRD of C/N-800 and C/N-Si-800 in embodiment 2.
Fig. 6 is the XPS figures of C/N-Si-800 in embodiment 3.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Si@SiO2Preparation：Articles of reference：Guangyu Zhao,Yufeng Meng,Naiqing Zhang,et
al.High storage performance of core-shell Si@C nanoparticle as lithium ion
battery anode material. Materials Letters,2013,96:170-173. (the Si@C nanos of core shell structure
The high storge quality research material bulletins of lithium ion battery negative material, 2013,96:170-173.), wherein Si and SiO2's
Mass ratio is 3:5；
Embodiment 1
Step 1：Take 5g acrylamides, 0.2g N,N methylene bis acrylamides and 0.054g potassium peroxydisulfates at room temperature
Stirring and dissolving is in 15mL deionized waters, by 1.5g Si@SiO after terminating2Ultrasonic disperse is used as aqueous phase in above-mentioned solution；
By 0.75g sorbester p17s stirring and dissolving in 75mL hexamethylenes, 0.5h is stirred, oil phase is used as；Then aqueous phase is added dropwise to oil phase
In, carry out anti-phase suspension under 500r/min mixing speeds, nitrogen protection in 9000r/min down cut 20min, after terminating and gather
Reaction is closed, reaction temperature is slowly increased to 55 DEG C from 30 DEG C, add the accelerator solution of 1mL dilutions after 0.5h into reaction system
(take 1mL N, N, N ', N '-tetramethylethylenediamine is diluted to 10mL, is used as accelerator solution), continue to react
1.5h.After reaction terminates, absolute ethyl alcohol is added into reaction system, polyacrylamide coated Si@SiO are obtained2It is compound micro-
Ball, using absolute ethyl alcohol cyclic washing 4 times, the consumption of each absolute ethyl alcohol is 150ml, 80 DEG C of dry 8h.
Step 2：Complex microsphere is warming up to 800 DEG C of high temperature, and constant temperature 2h, 5 DEG C/min of heating rate in argon atmosphere.
After cooling SiO is etched with HF2, after washing to neutral, drying, vacuum drying obtains nitrogen doped silicon charcoal composite negative pole material C/N-
Si-800。
Using the composite of preparation as lithium ion battery negative material active material and acetylene black, binding agent LA133
It is 8 according to mass ratio:1:1 ratio is mixed to be tuned into after slurry and is coated on Copper Foil, and the electrode after coating is dried at 60 DEG C
4 h, compressing tablet is carried out to it after cooling using powder compressing machine, and gauge pressure 10MPa is added the pole piece of above-mentioned compacting using sheet-punching machine
Work is into electrode slice (diameter：14mm), weigh, electrode slice is then dried in vacuo 12h at 120 DEG C, electrode slice is obtained.With this
Electrode slice is working electrode, and metal lithium sheet (thickness 0.2mm, diameter 14mm) is that polypropylene film is barrier film, concentration to electrode
For 1mol/L LiPF6+EC/DMC/EMC, (EC/DMC/EMC volume ratio is 1:1:1) solution is electrolyte, is assembled them into
CR2032 type buttons.
Electro-chemical test：Under 100mA/g current density, button type battery is carried out in 0.02-1.5V voltage range
Discharge and recharge, tests its cycle performance.
It is the FT-IR figures of acrylamide, polyacrylamide and C/N-Si-800 in embodiment 1 as shown in Figure 1.According to Fig. 1
Middle curve a is visible, 3338cm-1And 3163cm-1N-H asymmetric and symmetrical stretching vibration in respectively AM (acrylamide),
2813cm-1Corresponding to=CH2Stretching vibration, 1666cm-1Locate as the characteristic absorption peak of C=O in acid amides, and be often referred to as acyl
The band of amine I, 1610cm-1Locate the absworption peak for C=C, 1424cm-1Absorbed for C-N stretching vibration；AM polymerizations obtain PAM (poly- third
Acrylamide), curve b FT-IR collection of illustrative plates can be seen that from Fig. 1, in AM=CH2- CH is obtained after polymerization2-, therefore
2813cm-1Place's absworption peak is moved to 2930cm-1Place, and it is located at 1610cm originally-1Place belongs to C=C stretching vibration absworption peak
Almost vanish from sight, it can be seen that AM polymerization effect is fine.Curve c is that PAM cladding nano-silicons are obtained after high-temperature activation
C/N-Si-800 FT-IR figure, this it appears that C=O ,-CH on the curve2- and C-N absworption peak weaken significantly,
This is mainly due to the abundant charing under the conditions of material at high temperature.
The ball-type of complex microsphere is more regular as seen from Figure 2, there is part small particle microballoon, and microsphere surface is slightly thick
It is rough, because polyacrylamide and Si@SiO2Surface affinity it is not high cause, but almost soap-free emulsion polymeization between microballoon can
For use as composite negative pole material.
As seen from Figure 3, when using pure silicon as negative pole, the cyclical stability of negative material is very poor, and irreversible capacity is larger, fills
Specific discharge capacity is decayed rapidly, when only using C/N-800 as negative pole, and the cyclical stability of negative material is preferable, but charge and discharge
Electric specific capacity is very low all the time, it is impossible to meet the condition of height ratio capacity negative material, and C/N-Si-800 cyclical stability compared with
Good, first discharge specific capacity is 1 055.5mAh/g, and coulombic efficiency is 71.2% first, when persistent loop 40 times, except first
Circle circulation is outer, and C/N-Si-800 coulombic efficiency is higher, more than 99%, and after circulating 3 times, its charging and discharging capacity is
Higher than pure silicon negative pole, and when being recycled to 40 times, its specific discharge capacity is 557.4mAh/g, hence it is evident that find out C/N-Si-800 than pure
The service life cycle of silicium cathode is longer, and capability retention is more preferable.
As shown in figure 4, using thermogravimetric analysis determine silicon content, air atmosphere, temperature range be room temperature to 800 DEG C, rise
Warm speed is 10 DEG C/min, and principle is that under the high temperature conditions, the carbon dioxide in charcoal and air in material reacts, high
Remaining sample size is the content of silicon in composite after temperature calcining.
Nitrogen content is determined using XPS analysis, is 6.83%.
Embodiment 2
Step 1：The temperature for handling inverse suspension polymerization reaction is 50 DEG C, other conditions and step 1 phase in embodiment 1
Unanimously.
Step 2：By complex microsphere in argon atmosphere 800 DEG C of high-temperature activations, and constant temperature 2.5h, other conditions are with implementing
Step 2 in example 1 is identical.
Electro-chemical test step be the same as Example 1.
The first discharge specific capacity of material obtained by the present embodiment is that coulombic efficiency is 1050.9mAh/g first, first storehouse
Human relations efficiency is 71.3%.After circulation 20 times, capability retention is 63.5%.
Fig. 4 is after activating polyacrylamide and polyacrylamide cladding nano silicon material through 800 DEG C under an inert atmosphere
Obtained C/N-800 and C/N-Si-800 XRD, curve a results show the wide diffraction θ=25 ° of the angle of diffraction 2 and 43 °
Peak, is the characteristic absorption peak of amorphous carbon, corresponds respectively to graphite (002) and (100) crystal face；From curve b, C/N-Si-
In 800 in addition to the disperse peak for amorphous carbon occur, the diffraction maximum of silicon is also occurred in that near 2 θ=28,47,56 and 69 °, it
Correspond respectively to silicon (111), (220), (311) and (400) crystal face, it can be seen that, the charcoal bag of N doping is covered, and does not change
The crystalline structure of nano-silicon.
Embodiment 3
Step 1：The temperature for handling inverse suspension polymerization reaction is 53 DEG C, other conditions and step 1 phase in embodiment 1
Unanimously.
Step 2：By complex microsphere in argon atmosphere 700 DEG C of high-temperature activations, and constant temperature 3h, other conditions and embodiment 1
In step 2 it is identical.
Electro-chemical test step be the same as Example 1.
The first discharge specific capacity of material obtained by the present embodiment is that coulombic efficiency is 1027.4mAh/g first, first storehouse
Human relations efficiency is 70.9%.After circulation 20 times, capability retention is 61.9%.
Fig. 5 is the N1XPS figures of C/N-Si-700 in embodiment 3.As a result show, in the presence of 3 types in C/N-Si-700
Nitrogen, respectively pyridine type (398.2eV), pyrroles's type (399.8eV) and graphite mould (401.1eV).First principle research is pointed out
Pyridine type and pyrroles's type nitrogen in N doping Carbon Materials are conducive to improving the lithium ion storage capacity of material, and graphite mould nitrogen is then
Be conducive to improving the electric conductivity of Carbon Materials.
Embodiment 4
Step 1：The temperature for handling inverse suspension polymerization reaction is 50 DEG C, other conditions and step 1 phase in embodiment 1
Unanimously.
Step 2：By complex microsphere in argon atmosphere 750 DEG C of high-temperature activations, and constant temperature 2h, other conditions and embodiment 1
In step 2 it is identical.
Electro-chemical test step be the same as Example 1.
The first discharge specific capacity of material obtained by the present embodiment is that coulombic efficiency is 1041.3mAh/g first, first storehouse
Human relations efficiency is 71.2%.After circulation 20 times, capability retention is 62.4%.
Comparative example
Step 1：Except in reaction raw materials without Si@SiO2Outside, the step 1 in other conditions be the same as Example 1 is obtained
To polyacrylamide microsphere.
Step 2：By polyacrylamide microsphere in argon atmosphere 800 DEG C of high-temperature activations, and constant temperature 2h, heating rate 5
DEG C/min, obtain C/N-800.
C/N-800 discharge and recharge data and XRD analysis are shown in Fig. 3, Fig. 4 respectively in comparative example.
Claims (9)
1. a kind of nitrogen doped silicon charcoal composite negative pole material, it is characterised in that：Including nano Si sandwich layer and it is wrapped in nano Si core
The N doping layer of charcoal of layer periphery, the wherein mass content of silicon are (27.32 ± 0.2) %.
2. nitrogen doped silicon charcoal composite negative pole material as claimed in claim 1, it is characterised in that：The average grain diameter of composite is
10.1±0.5μm。
3. the preparation method of the nitrogen doped silicon charcoal composite negative pole material described in claim 1 or 2, it is characterised in that：First pass through molten
Sol-gel is in one layer of SiO of nano Si Surface coating2, obtain Si@SiO2；Then polypropylene is utilized by inverse suspension polymerization again
Acid amides coated Si@SiO2, SiO is etched using HF after high-temperature activation2, obtain nitrogen doped silicon charcoal composite negative pole material.
4. the preparation method of nitrogen doped silicon charcoal composite negative pole material as claimed in claim 3, it is characterised in that：Anti-phase suspension gathers
It is acrylamide to close monomer used, and crosslinking agent is N, and N- methylene-bisacrylamides, initiator is potassium peroxydisulfate, and coagulant is N,
N, N ', N '-tetramethylethylenediamine.
5. the preparation method of nitrogen doped silicon charcoal composite negative pole material as claimed in claim 4, it is characterised in that：Si@SiO2With third
The mass ratio of acrylamide monomer is (0.3 ± 0.1):1.
6. the preparation method of the nitrogen doped silicon charcoal composite negative pole material as described in claim 3-4 any one, it is characterised in that：
Carry out in accordance with the following steps successively：
1) by sol-gal process in one layer of SiO of nano Si Surface coating2, obtain Si@SiO2, wherein Si and SiO2Mass ratio
For 3:(5±1)；
2) by acrylamide, N, N- methylene-bisacrylamides and potassium peroxydisulfate at room temperature stirring and dissolving in deionized water,
Then by Si@SiO2Ultrasonic disperse is used as aqueous phase in wherein；Wherein, acrylamide, N, N- methylene-bisacrylamides, over cure
Sour potassium, water, Si@SiO2Mass ratio be：5:(0.2±0.1):(0.054±0.01):(15±2):(1.5 ± 0.2), Si@
SiO2Mass ratio with acrylamide is 0.3:1；
3) by sorbester p17 stirring and dissolving in hexamethylene, 0.5 ± 0.1h is persistently stirred after dissolving, oil phase is used as；Wherein, sorbester p17
Mass ratio with acrylamide is (0.15 ± 0.02):1, the consumption of hexamethylene is every gram of sorbester p17 with 100 ± 5mL；
4) aqueous phase is added dropwise in oil phase, in 9000 ± 500r/min, 20 ± 5min of down cut, then stirred in 500 ± 100r/min
Speed, the lower progress inverse suspension polymerization reaction of nitrogen protection are mixed, reaction temperature is slowly increased to 50-60 DEG C in 0.5h from room temperature,
Heated up 0.5 ± 0.1h of follow-up continuous stirring in place, and accelerator solution is then added into reaction system, continues to react 1.5 ± 0.2h,
After reaction terminates, absolute ethanol washing is added into reaction system, 80 ± 5 DEG C of dry 8 ± 1h obtain polyacrylamide cladding
Si@SiO2Complex microsphere, wherein accelerator solution is the N that concentration is 0.1 ± 0.01g/mL, N, N ', N '-tetramethylethylenediamine
The aqueous solution, N, N, N ', the mass ratio of N '-tetramethylethylenediamine and acrylamide is 0.02:(1±0.1)；
5) complex microsphere is activated in argon atmosphere high temperature, SiO is etched with HF after cooling2, washing to neutrality, 80 ± 5 DEG C of vacuum
Dry 8 ± 1h and obtain nitrogen doped silicon charcoal composite negative pole material.
7. the preparation method of nitrogen doped silicon charcoal composite negative pole material as claimed in claim 6, it is characterised in that：High-temperature activation
For：Complex microsphere is warming up to 700-800 DEG C, constant temperature 2-3h heats up as 5 ± 1 DEG C/min of speed.
8. the preparation method of nitrogen doped silicon charcoal composite negative pole material as claimed in claim 6, it is characterised in that：Step 3) in oil
It must mutually prepare and be completed at 30 ± 5 DEG C.
9. the preparation method of nitrogen doped silicon charcoal composite negative pole material as claimed in claim 8, it is characterised in that：Step 4) in
Heat up and be slowly increased to 50-60 DEG C from 30 ± 5 DEG C in 0.5h for reaction temperature.
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| CN107946558A (en) * | 2017-11-05 | 2018-04-20 | 长沙秋点兵信息科技有限公司 | A kind of preparation method of lithium ion battery silicon-carbon composite material |
| CN107978750A (en) * | 2017-11-27 | 2018-05-01 | 江西师范大学 | The forming method of anode material of lithium-ion battery |
| CN109786711A (en) * | 2019-01-23 | 2019-05-21 | 电子科技大学 | A kind of preparation method of porous carbon skeleton cladding tin combination electrode material |
| CN110752352A (en) * | 2018-07-09 | 2020-02-04 | 湖南师范大学 | Preparation method for carbon-coated silicon negative electrode material synthesized by aid of boron-nitrogen-doped polymer |
| CN114171728A (en) * | 2021-11-30 | 2022-03-11 | 陕西科技大学 | Three-dimensional porous silicon-carbon composite material, preparation method and application thereof |
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| CN104176725A (en) * | 2014-09-02 | 2014-12-03 | 陈大明 | Method for fixing carbon in saccharides and preparing high-purity carbon (graphite) material |
| CN106450251A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Anode material for Li-ion batteries and preparation method thereof |
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| CN107946558A (en) * | 2017-11-05 | 2018-04-20 | 长沙秋点兵信息科技有限公司 | A kind of preparation method of lithium ion battery silicon-carbon composite material |
| CN107978750A (en) * | 2017-11-27 | 2018-05-01 | 江西师范大学 | The forming method of anode material of lithium-ion battery |
| CN107978750B (en) * | 2017-11-27 | 2020-07-24 | 江西师范大学 | Method for forming negative electrode material of sodium ion battery |
| CN110752352A (en) * | 2018-07-09 | 2020-02-04 | 湖南师范大学 | Preparation method for carbon-coated silicon negative electrode material synthesized by aid of boron-nitrogen-doped polymer |
| CN110752352B (en) * | 2018-07-09 | 2023-02-28 | 湖南师范大学 | Preparation method for carbon-coated silicon negative electrode material synthesized by aid of boron-nitrogen-doped polymer |
| CN109786711A (en) * | 2019-01-23 | 2019-05-21 | 电子科技大学 | A kind of preparation method of porous carbon skeleton cladding tin combination electrode material |
| CN114171728A (en) * | 2021-11-30 | 2022-03-11 | 陕西科技大学 | Three-dimensional porous silicon-carbon composite material, preparation method and application thereof |
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