CN105428611B - A kind of Porous hollow composite negative pole material and its preparation method and application - Google Patents
A kind of Porous hollow composite negative pole material and its preparation method and application Download PDFInfo
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- CN105428611B CN105428611B CN201510737893.2A CN201510737893A CN105428611B CN 105428611 B CN105428611 B CN 105428611B CN 201510737893 A CN201510737893 A CN 201510737893A CN 105428611 B CN105428611 B CN 105428611B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of preparation method of high-performance Porous hollow composite negative pole material, by introducing SiO on the nanometer anode material surface of high power capacity2Layer introduces uniform carbon-coating by in-situ polymerization phenolic resin, is then allowed to surface cross-linked polymeric high molecular polymer and soft template again as sacrifice layer, by high temperature cabonization and goes the method for template to prepare high-performance Porous hollow composite negative pole material.The invention also discloses a kind of high-performance Porous hollow composite negative pole material and its application.The characteristics of present invention is according in lithium cell cathode material charge and discharge cycles, by the carbon-coating being evenly coated outside the intermediate layer of active material, in the uniform meso-hole structure of outer carbon-coating medium design, so as to effectively improve the chemical property of electrode material.Preparing raw material of the present invention is cheap, and operating procedure is simple, and high income, the charge-discharge performance of material are excellent, are easy to industrialized production.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of high-performance porous-hollow compound
Negative material and its preparation method and application.
Background technology
Lithium ion battery has that open-circuit voltage is high, energy density is big, long service life, memoryless effect, of low pollution and
The advantages of self-discharge rate is little, it is better than other traditional secondary batteries on overall performance, is considered as unanimously various portable electrics
Sub- equipment and ideal power supply used for electric vehicle.Although conventional lithium ion battery negative material graphite good cycling stability with
And cost performance is higher, but as its charging and discharging capacity is relatively low, volume and capacity ratio is even more no advantage, it is difficult to meet dynamical system
System is particularly the requirement of electric motor car and hybrid electric vehicle to cell high-capacity.Therefore exploitation is with height ratio capacity, high charge-discharge
The great urgency of novel cathode material for lithium ion battery of efficiency, long circulation life.
In the research of new non-carbon negative material, the pure metals such as silicon, tin, germanium, metal oxide and composition metal
Oxide material is because increasingly attracting attention with higher theoretical embedding lithium capacity.If the negative material of these high power capacity can reach
Degree of being practical, will be such that the range of application of lithium ion battery widens significantly.But, the negative material of these high power capacity is mostly electric
Conductance is relatively low, and under the conditions of high level removal lithium embedded, there is serious bulk effect, causes the cyclical stability of electrode poor.
For the shortcoming of volume efficiency and the low conductivity of the negative material of these high power capacity, by it with elasticity, stable performance and
The carrier for conducting electricity very well is combined, the Volume Changes of buffers active material, improves its circulation steady while being to maintain high power capacity
Qualitatively effective way.Carbon is due to possessing lighter quality, preferable electric conductivity, relatively low intercalation potential, body during deintercalation
Many advantages, such as product change is little and cheap etc. is widely used in anode material.
In order to further improve the performance of base material of cathode material, in addition to carbon coating being carried out to active material and is processed, compound
Increase certain pore structure to be necessary in material.Because it is swollen that the presence of these pore structures acts not only as Si volumes
The swollen buffer zone with contraction, maintains the complete and stability of electrode structure so as to reduce the deformation of electrode, moreover it is possible to for active matter
High contact area is provided between matter and electrolyte, the diffusion rate of lithium ion is improved, so as to further improve combination electrode
Chemical property.By Si nano particles, phenolic resin and business Nano-meter SiO_2 is blended2, go via high temperature cabonization and a step
The process of template prepares the porous Si/ porous carbon composite of cushion space.Si nano particles are embedded in porous carbon
In network structure, hollow core shell structure is formed.Prepared combination electrode has storage lithium performance well, remains to protect after 80 circulations
The reversible capacity in 963 mAh/g is held, under the electric current of 2000 mA/g, remains to keep the reversible capacity of 721 mAh/g
（Electrochim. Acta, 125, 206–217, 2014）, result of study is that the design of the present invention and feasibility have made weight
The place mat wanted.
The content of the invention
Goal of the invention：First technical problem to be solved of the present invention there is provided a kind of high-performance porous-hollow
The preparation method of composite negative pole material.
Second technical problem to be solved of the present invention there is provided a kind of high-performance porous-hollow composite negative pole material
Material.
3rd technical problem to be solved of the present invention there is provided a kind of high-performance porous-hollow composite negative pole material
Application of the material in terms of combination electrode is prepared.
Technical scheme：In order to solve above-mentioned technical problem, the invention provides a kind of high-performance porous-hollow composite negative pole
The preparation method of material, by introducing SiO on the nanometer anode material surface of high power capacity2Layer is gathered by situ as sacrifice layer
Close phenolic resin and introduce uniform carbon-coating, be then allowed to surface cross-linked polymeric high molecular polymer and soft template again, by pyrocarbon
Change and go the method for template to prepare high-performance porous-hollow composite negative pole material.
Specifically include following steps：
1）Uniform silicon dioxide layer is prepared on the nanometer anode material surface of high power capacity；
2）In the aqueous solution that the negative material deionized water containing silicon dioxide layer of above-mentioned preparation and ethanol are mixed, ultrasound
Dispersion, stirs；A certain amount of surfactant cetyl trimethylammonium bromide is subsequently adding, resorcinol and ammonia is added
Then it is placed in 45 DEG C of 30～60 min of stirring in oil bath, a certain amount of formalin by water, 30～60 min of ultrasonic agitation
In adding above-mentioned mixed solution, suction filtration after 45 DEG C of stirring certain hours is maintained, be washed with deionized water 3～5 times, 70 DEG C of vacuum are done
Dry 3～5 h, prepares the composite containing novolac resin layer cladding；
3）The composite containing novolac resin layer cladding will be prepared to be re-dispersed in a certain amount of deionized water, ultrasound
Dispersion；Under condition of ice bath, aniline monomer is added dropwise, ultrasonic disperse is uniform, a certain amount of Pluronic F127 of addition, stirring and dissolving,
Add a certain amount of plant acid solution；
4）By step 3）Mixed solution first stir under ice bath, adjust pH value, the aqueous solution containing oxidant be then added dropwise,
It is stirred overnight under ice bath, suction filtration, after cleaning, is dried to obtain compound；
5）By step 4）Compound under shielding gas high-temperature process, with HF acid treatments prepare high-performance porous-in
Empty composite negative pole material.
The nanometer anode material of the high power capacity is nano silica fume, germanium powder, glass putty；Or nano-oxide powder includes titanium dioxide
Tin, tungsten oxide, zinc oxide, indium oxide；Or the one kind in nano composite metal oxide zinc manganate, cobalt acid manganese, Manganese Ferrite powder
Or it is various.
Further, described loose structure is that mesoporous, hollow interporal lacuna is 10-50 nm.
Further, carbon and the nanometer anode material of high power capacity in the high-performance porous-hollow composite negative pole material
Mass ratio is 1:10～1:1, carbon can be played under the ratio and improved electrical conductivity in the composite, suppressed the tribute of volumetric expansion
Offer, can guarantee that prepared combination electrode has higher specific capacity again.
Further, the step 3）The addition of middle aniline monomer is the quality of the nanometer anode material of high power capacity
0.5～3 times, step 4）1.5～3 times for the quality of aniline monomer of the addition of middle oxidant, oxidant are (NH4)2S2O8。
Further, the step 5）In high-temperature process be：600～1000 DEG C are entered in a vacuum or inert atmosphere
OK, inert atmosphere is Ar, Ar/H2Gaseous mixture or He.
Further, the step 5）The consumption of HF acid is 1～3%, and process time is 5～120 min.
The high-performance porous that above-mentioned preparation method is prepared-hollow composite negative pole material.
Above-mentioned high-performance porous-application of the hollow composite negative pole material in terms of combination electrode is prepared.
Beneficial effect：The characteristics of present invention is according in lithium cell cathode material charge and discharge cycles, by active material
The carbon-coating being evenly coated outside intermediate layer, in the uniform meso-hole structure of outer carbon-coating medium design, so as to effectively improve electrode material
The chemical property of material.Preparing raw material of the present invention is cheap, and operating procedure is simple, and high income, the charge-discharge performance of material are excellent, just
In industrialized production.The present invention improves obvious to the cycle performance of active material.Additionally, solvent used in the present invention is water,
Environmental friendliness, and it is reproducible, with low cost, with preferable scale application potential, industrial prospect is good.
Description of the drawings
Preparation technology schematic flow sheets of the Fig. 1 for high-performance porous-hollow composite negative pole material；
TEM photos of the Fig. 2 for sample prepared by embodiment 1 ~ 3；(a/b) it is high-performance porous-hollow Si bases composite negative pole
The TEM figures of material, (c) are respectively high-performance porous-hollow SnO with (d)2Base and ZnFe2O4The TEM figures of composite negative pole material；
Fig. 3 is the high-performance porous-electrode prepared by hollow Si bases composite negative pole material of the preparation of embodiment 1 in 400 mA
g-1Charging and discharging currents density under cycle performance test curve；
Fig. 4 is high-performance porous-hollow SnO prepared by embodiment 22Electrode prepared by base composite negative pole material is 400
mA·g-1Charging and discharging currents density under cycle performance test curve；
Fig. 5 is high-performance porous-hollow ZnFe prepared by embodiment 32O4Electrode prepared by base composite negative pole material is 400
mA·g-1Charging and discharging currents density under cycle performance test curve.
Specific embodiment
Embodiment of the present invention is further described below in conjunction with accompanying drawing：Following examples are with technical solution of the present invention
Premised under implemented, give detailed embodiment and specific operating process, but protection scope of the present invention do not limited
In following embodiments.
Granularity is adopted in following examples for the active material of 500 below nm, and in accordance with the technique shown in Fig. 1
Flow implementation.
Embodiment 1
1）1.0g Si powder 600 DEG C of high-temperature process 1h in Muffle furnace are taken, SiO is prepared2The Si materials of layer cladding；
2）0.2 g is taken containing SiO2The Si materials of layer cladding are scattered in the deionized water and 71.4 mL of 100 mL, 28.6 mL
In the aqueous solution of ethanol mixing, 1 h of ultrasonic agitation.1.2 g cetyl trimethylammonium bromides（CTAB）, 0.175 g isophthalic
Diphenol, the ammoniacal liquor of 0.1 mL, in adding above-mentioned solution, 30 min of ultrasonic agitation.Then it is placed in into 45 DEG C of stirrings 30 in oil bath
Min, adds the formalin of 0.15 mL in above-mentioned mixed solution, after maintaining 45 DEG C of stirring 1h, suction filtration immediately, spend from
Son washing 3 times, 70 DEG C of 3 h of vacuum drying, prepares the composite of novolac resin layer cladding；
3）The above-mentioned composite 0.1g for preparing novolac resin layer cladding is re-dispersed into into 50 mL deionized waters
In, ultrasonic disperse；Under condition of ice bath, 0.2mL aniline monomers are added dropwise, ultrasonic disperse is uniform, adds 0.2g Pluronic
F127, stirring and dissolving add 0.5mL plant acid solutions, ultrasonic agitation 1h.Then the pH value for adjusting solution with concentrated hydrochloric acid is 3 left
The right side, continues stirring 20min.
4）10 mL are prepared containing (NH4)2S2O8 The aqueous solution of 0.5g, by the above-mentioned solution of addition in.Keep condition of ice bath,
Reaction 12 hours.By mixture suction filtration, it is washed with deionized 3 times, is dried, grinding obtains compound；
5）Above-mentioned sintered powder is immersed in 10 mL and contains 0.2mL's by compound 800 degree of 3h sintering under Ar gas
In the HF aqueous solution, 10 min remove template, wash again three times after suction filtration, and drying prepares high-performance porous-hollow Si bases
Composite negative pole material, the hollow interporal lacuna of the composite for preparing are about 15nm, the carbon of the composite for preparing
It is about 1 with the ratio of Si：1.5.
6）After the high-performance porous for obtaining after by sintering-hollow Si bases composite negative pole material is fully ground, and carbon black and
Carboxymethylcellulose calcium is well mixed according to 60: 20: 20 ratio, 60 DEG C of 4 h of vacuum drying after film, is prepared multiple
Composite electrode.By electrode in 2025 battery cases, it is to electrode, with polyethylene film as barrier film, with 1M LiPF with lithium piece6 EC/DEC
(v/v=1/1) carries out constant current charge-discharge test for electrolyte assembled battery.Test result refers to experimental example.
Embodiment 2
1）Take SnO2Nano particle（50-70 nm）0.5g, is prepared containing SiO by Stober methods2The SnO of layer cladding2
Material；
2）0.4 g is taken containing SiO2The SnO of layer cladding2Material be scattered in 100 mL, 28.6 mL deionized water and
In the aqueous solution of 71.4 mL ethanol mixing, 1 h of ultrasonic agitation.2.4 g cetyl trimethylammonium bromides, 0.35 g isophthalic
Diphenol, the ammoniacal liquor of 0.1 mL, in adding above-mentioned solution, ultrasonic agitation 60min.Then it is placed in into 45 DEG C of stirrings in oil bath
60min, adds the formalin of 0.3 mL in above-mentioned mixed solution, after maintaining 45 DEG C of stirring 1h, suction filtration immediately, spend from
Son washing 3 times, 70 degree of vacuum drying 5h, prepares the composite of novolac resin layer cladding；
3）By it is above-mentioned prepare novolac resin layer cladding 0.2 g of composite material be re-dispersed into 50 mL go from
In sub- water, ultrasonic disperse；Under condition of ice bath, 0.2mL aniline monomers are added dropwise, ultrasonic disperse is uniform, adds 0.2g Pluronic
F127, stirring and dissolving add 0.5mL plant acid solutions, ultrasonic agitation 1h.Then the pH value for adjusting solution with concentrated hydrochloric acid is 3 left
The right side, continues stirring 20min.
4）10 mL are prepared containing (NH4)2S2O8 The aqueous solution of 0.6g, by the above-mentioned solution of addition in.Keep condition of ice bath,
Reaction 12 hours.By mixture suction filtration, it is washed with deionized 3 times, is dried, grinding obtains compound；
5）Compound is in Ar/H2Under gas, 500 degree sinter for 6 hours, above-mentioned sintered powder is immersed in 10mL and is contained
In the HF aqueous solution of 0.2mL 120min remove template, washed after suction filtration again three times, drying prepare high-performance porous-
Hollow SnO2Base composite negative pole material, the hollow interporal lacuna of the composite for preparing are about 20nm, and what is prepared answers
The carbon and SnO of condensation material2Ratio be about 1：3.
6）By the high-performance porous obtained after sintering-hollow SnO2After base composite negative pole material material is fully ground, and charcoal
Black and carboxymethylcellulose calcium is well mixed according to 60: 20: 20 ratio, and after film, 60 DEG C of 4 h of vacuum drying, are prepared into
To combination electrode.By electrode in 2025 battery cases, it is to electrode, with polyethylene film as barrier film, with 1M LiPF with lithium piece6
EC/DEC (v/v=1/1) carries out constant current charge-discharge test for electrolyte assembled battery.Test result refers to experimental example.
Embodiment 3
1）Take ferrous acid zinc nanoparticles（50 nm）0.5 g, is prepared containing SiO by Stober methods2The ferrous acid of layer cladding
Zinc material；
2）0.4 g is taken containing SiO2Layer cladding ferrous acid Zinc material be scattered in 100 mL, 28.6 mL deionized water and
In the aqueous solution of 71.4 mL ethanol mixing, 1 h of ultrasonic agitation.2.4 g cetyl trimethylammonium bromides（CTAB）, 0.35
G resorcinols, the ammoniacal liquor of 0.1 mL, in adding above-mentioned solution, 45 min of ultrasonic agitation.Then it is placed in oil bath 45 DEG C to stir
45min is mixed, the formalin of 0.3 mL is added in above-mentioned mixed solution, after maintaining 45 DEG C of stirring 1h, suction filtration, spends immediately
Ion is washed 3 times, and 70 degree of 3 h of vacuum drying prepare the composite for obtaining novolac resin layer cladding；
3）By prepare obtain novolac resin layer cladding composite 0.2g be re-dispersed into 50 mL deionized waters
In, ultrasonic disperse；Under condition of ice bath, 0.2mL aniline monomers are added dropwise, ultrasonic disperse is uniform, adds 0.2g Pluronic
F127, stirring and dissolving add 0.5mL plant acid solutions, ultrasonic agitation 1h.Then the pH value for adjusting solution with concentrated hydrochloric acid is 3 left
The right side, continues 20 min of stirring.
4）10 mL are prepared containing (NH4)2S2O8 The aqueous solution of 0.6 g, by the above-mentioned solution of addition in.Keep ice bath bar
Part, reacts 12 hours.By mixture suction filtration, it is washed with deionized 3 times, is dried, grinding obtains compound；
5）Compound is sintered for 600 DEG C under He gas for 5 hours, above-mentioned sintered powder is immersed in 10 mL and contains 0.2
In the HF aqueous solution of mL, 100min removes template, washs again three times after suction filtration, and drying prepares high-performance porous-hollow
ZnFe2O4Base composite negative pole material, the hollow interporal lacuna of the composite for preparing is about 20 nm, and what is prepared answers
The carbon and SnO of condensation material2Ratio be about 1：2.5.
6）By the high-performance porous obtained after sintering-hollow ZnFe2O4After base composite negative pole material is fully ground, and carbon black
And carboxymethylcellulose calcium is well mixed according to 60: 20: 20 ratio, after film, 60 DEG C of 4 h of vacuum drying, prepare
Combination electrode.By electrode in 2025 battery cases, it is to electrode, with polyethylene film as barrier film, with 1M LiPF with lithium piece6 EC/
DEC (v/v=1/1) carries out constant current charge-discharge test for electrolyte assembled battery.Test result refers to experimental example.
Experimental example：
Below by TEM photos to the pattern of composite and by cycle performance test preparation of the present invention is combined
The chemical property of material is tested and is characterized.
1st, tem analysis
TEM photos of the Fig. 2 for sample and associated sample prepared by the embodiment of the present invention 1 ~ 3.Fig. 2 (a) and (b) are Si bases
The TEM photos of composite, it can be seen that the particle size range of Si is 50-120 nm, and spherical shape is presented.Si particles are equal
Even is coated in the lattice of porous carbon.Between Si and carbon, there are the uniform space layer of an about 15nm, whole composite wood section
Uniform porous-hollow structure is presented.C () and (d) is respectively high-performance porous-hollow SnO2Base and ZnFe2O4Composite negative pole material
Material TEM figure, by figure as can be seen that diameter be about 50-70 nm SnO2Or ZnFe2O4Porous carbon is coated on uniformly
In lattice, there is uniform space structure between particle and carbon.
2nd, cycle performance test
Fig. 3 is the high-performance porous-electrode prepared by hollow Si bases composite negative pole material of embodiment 1 in 400 mAg-1's
Cycle performance test curve under charging and discharging currents density.It can be seen that the capacity attenuation speed for not being wrapped by Si is very big on figure,
By 3795 initial mAhg-146 mAhg are rapidly decayed to after 100 circulations-1.And Si/C composite electrodes
Cycle performance is significantly improved, and remains to keep 1302 mAhg after 100 circulations-1Discharge capacity, capacity attenuation
Speed is only 0.06%（Relative to second discharge capacity）.
High-performance porous-hollow SnOs of the Fig. 4 for embodiment 22Prepared by base composite negative pole material, electrode is in 400 mAg-1
Charging and discharging currents density under cycle performance test curve, it can be seen that relative to the SnO not being wrapped by figure2The electricity of material
Pole, it is multiple and after electrode show larger performance improvement, after 100 circulations, discharge capacity is from 171 mAhg-1Improve to 697
mAh·g-1。
High-performance porous-hollow ZnFes of the Fig. 5 for embodiment 32O4Prepared by base composite negative pole material, electrode is in 400 mA
g-1Charging and discharging currents density under cycle performance test curve, it can be seen that relative to the ZnFe not being wrapped by figure2O4
The electrode of material, it is multiple and after electrode equally show larger performance improvement, after 100 circulations, discharge capacity is from 73 mAh
g-1Improve to 608 mAhg-1。
In sum, in porous-hollow composite material that prepared by the present invention, nano particle is successfully coated on material with carbon element
In, porous and hollow structure cause active material particle great volumetric expansion in charge and discharge process effectively to be pressed down
System, so as to greatly improve the cycle performance of material.
Claims (5)
1. the preparation method of a kind of porous-hollow composite negative pole material, it is characterised in that by the nanometer negative pole material in high power capacity
Material surface introduces SiO2Layer introduces uniform carbon-coating by in-situ polymerization phenolic resin, is then allowed to surface and hands over again as sacrifice layer
Connection polymerization macromolecule polymer polyanaline and soft template, by high temperature cabonization and goes the method for template to prepare porous-hollow
Composite negative pole material；
Specifically include following steps：
1）Uniform silicon dioxide layer is prepared on the nanometer anode material surface of high power capacity；
2）The negative material containing silicon dioxide layer of above-mentioned preparation is added in the aqueous solution of deionized water and ethanol mixing, is surpassed
Sound disperses, and stirs；A certain amount of surfactant cetyl trimethylammonium bromide is subsequently adding, resorcinol and ammonia is added
Then it is placed in 45 DEG C of 30～60 min of stirring in oil bath, a certain amount of formalin by water, 30～60 min of ultrasonic agitation
In adding above-mentioned mixed solution, suction filtration after 45 DEG C of stirring certain hours is maintained, be washed with deionized water 3～5 times, 70 DEG C of vacuum are done
Dry 3～5 h, prepares the composite containing novolac resin layer cladding；
3）The composite containing novolac resin layer cladding will be prepared to be re-dispersed in a certain amount of deionized water, ultrasound point
Dissipate；Under condition of ice bath, aniline monomer is added dropwise, ultrasonic disperse is uniform, adds triblock polymer Pluronic F127, stirring
Dissolving, adds a certain amount of plant acid solution to obtain mixed solution；
4）By step 3）Mixed solution first stir under ice bath, adjust pH value, the aqueous solution containing oxidant be then added dropwise, in ice
It is stirred overnight under bath, suction filtration, after cleaning, is dried to obtain compound；
5）By step 4）Compound under shielding gas high-temperature process, prepare porous-hollow composite negative pole with HF acid treatments
Material；
Wherein, the nanometer anode material of the high power capacity is nano silica fume, germanium powder, glass putty；Or nano-oxide powder includes dioxy
Change tin, tungsten oxide, zinc oxide, indium oxide；Or in nano composite metal oxide zinc manganate, cobalt acid manganese, Manganese Ferrite powder
Plant or various, described loose structure is that mesoporous, hollow interporal lacuna is 10-50 nm, described porous-hollow composite negative pole
In material, carbon and the mass ratio of the nanometer anode material of high power capacity are 1:10～1:1, the step 3）The addition of middle aniline monomer
Measure nanometer anode material for high power capacity 0.5～3 times of quality, step 4）The addition of middle oxidant is aniline monomer
1.5～3 times of quality, oxidant are (NH4)2S2O8。
2. the preparation method of a kind of porous according to claim 1-hollow composite negative pole material, it is characterised in that described
Step 5）In high-temperature process be：600～1000 DEG C are carried out in a vacuum or inert atmosphere, and inert atmosphere is Ar, Ar/H2It is mixed
Close gas or He.
3. the preparation method of a kind of porous according to claim 1-hollow composite negative pole material, it is characterised in that described
Step 5）The consumption of HF acid is 1～3%, and process time is 5～120 min.
4. the porous that the preparation method described in claim 1 is prepared-hollow composite negative pole material.
5. the porous described in claim 4-application of the hollow composite negative pole material in terms of combination electrode is prepared.
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| CN201510737893.2A CN105428611B (en) | 2015-11-03 | 2015-11-03 | A kind of Porous hollow composite negative pole material and its preparation method and application |
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| CN105428611B true CN105428611B (en) | 2017-04-05 |
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| CN105932284B (en) * | 2016-07-13 | 2019-01-22 | 盐城工学院 | A kind of close cladded type composite material and preparation method of mesoporous carbon and application |
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| CN108448090A (en) * | 2018-03-19 | 2018-08-24 | 哈尔滨工业大学 | A kind of preparation method of lithium battery silicon-carbon composite material |
| CN109713257B (en) * | 2018-12-06 | 2021-12-10 | 盐城工学院 | High-performance Si @ SnO2@ C composite material and preparation method and application thereof |
| CN109817962A (en) * | 2019-04-02 | 2019-05-28 | 福建蓝海黑石新材料科技有限公司 | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method of phenolic resin modification |
| CN110197900A (en) * | 2019-06-20 | 2019-09-03 | 厦门大学 | A kind of Si-C composite material and its preparation method and application |
| CN110436440A (en) * | 2019-07-22 | 2019-11-12 | 华南农业大学 | A kind of hollow ordered mesoporous carbon nanospheres of noble metal and the preparation method and application thereof |
| CN111600005B (en) * | 2020-06-16 | 2022-04-22 | 广西师范大学 | Preparation method of lithium ion battery negative electrode material porous Si/C composite material |
| CN112786900B (en) * | 2021-02-03 | 2022-01-28 | 江西理工大学 | Zinc-air cell with embedded Fe2Nitrogen-rich phosphorus carbon spheres of P nanocrystalline and preparation method thereof |
| CN113707858A (en) * | 2021-08-23 | 2021-11-26 | 上海颂柏智能技术开发中心 | Porous carbon-silicon composite negative electrode material and preparation method thereof |
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