CN105047877A - Negative active material and preparation method and application thereof - Google Patents
Negative active material and preparation method and application thereof Download PDFInfo
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- CN105047877A CN105047877A CN201510399074.1A CN201510399074A CN105047877A CN 105047877 A CN105047877 A CN 105047877A CN 201510399074 A CN201510399074 A CN 201510399074A CN 105047877 A CN105047877 A CN 105047877A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a negative active material and a preparation method and application thereof. The negative active material comprises silica nanoparticles and a carbon-based material layer, wherein the carbon-based material layer is formed on at least part of outer surfaces of the silica nanoparticles, and gaps exist between at least one part of the carbon-based material layer and the outer surfaces of the silica nanoparticles. A battery prepared from the negative active material is high in capacity, good in circularity and long in service life, and is difficult to attenuate.
Description
Technical field
The present invention relates to electrochemical field, particularly, relate to negative active core-shell material and its preparation method and application, more specifically, relate to negative active core-shell material, prepare the method for negative active core-shell material, negative pole and battery.
Background technology
Lithium ion battery is owing to having that open circuit voltage is high, energy density is large, self-discharge rate is little and the advantage such as pollution-free and be widely used in the fields such as electronic equipment, electronic traffic, Aero-Space, military affairs, medical science.The charge and discharge process of lithium ion battery, based on the repeatedly embedding of lithium ion between positive and negative pole material and deintercalation.At present, business-like lithium ion battery mainly adopts carbon materials as negative pole, and graphite is beneficial to the embedding of lithium ion due to its layer structure and deviates from and obtain to apply the most widely.But the theoretical specific capacity of graphite is only 372mAh/g, relatively low, cannot meet growing high power capacity, high power requirements.Therefore, find the material of novel height ratio capacity, become the important probing direction of lithium ion battery negative research.
In non-carbon material, silicon, due to its advantage such as higher theoretical specific capacity (4200mAh/g) and discharge potential is low, natural rich reserves, becomes the most potential lithium ion battery negative material of alternative graphite.But body silicon materials are at Lithium-ion embeding and deviate from process, have the change in volume up to 300%, this can cause electrode structure to destroy, electrical connection was lost efficacy, active material continues the problems such as consumption, and finally cause battery capacity to decay rapidly, cycle performance worsens.
At present, a kind of main method improving silicium cathode is by silicon materials nanometer, as nano thin-film, nano wire, nano particle etc., the silicon of nanometer better can discharge the stress of change in volume generation, the space of volumetric expansion is provided simultaneously, but due to the intrinsic conductivity of silicon low, the silicon of nanometer still has obvious capacity attenuation over numerous cycles, and cell power density is also lower.M.Holzapfel, N.Liu etc. utilize the composite material of silicon and carbon, are not only beneficial to the electron conduction of reinforcing material, and simultaneously the light weight of material with carbon element, ductile characteristic are also conducive to Stress Release.But the shortcoming that above-mentioned negative material ubiquity tap density is low, volume and capacity ratio is low, limit the capacity of lithium ion battery on unit chip area and power-performance, in addition, be also difficult to and microelectronics manufacture compatible.
Therefore, the material preparing lithium ion battery awaits further research.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.For this reason, one object of the present invention be to propose that a kind of battery capacity is high, cyclicity good, long service life and the high battery of power.
According to an aspect of the present invention, the invention provides a kind of negative active core-shell material.According to embodiments of the invention, this negative active core-shell material comprises: nano silicon particles; And carbon base material layer, described carbon base material layer is formed at least part of outer surface of described nano silicon particles, wherein, described carbon base material layer there is space at least partially and between the outer surface of described nano silicon particles.
The discovery that inventor is surprised, space is there is between the carbon base material layer of negative active core-shell material of the present invention and the outer surface of nano silicon particles, this space is in charging, discharging electric batteries process, silicon volumetric expansion provides headspace, be conducive to keeping the structural integrity of negative active core-shell material, thus the capacity of battery is high and not easily decay, cyclicity is good, long service life.
According to another aspect of the invention, the invention provides a kind of method preparing negative active core-shell material.According to embodiments of the invention, the method comprises: be hydrolyzed nano silicon particles oxidation processes, to obtain the comprehensive silicon particle with silica surface; In described comprehensive silicon particle, add carbon source, mix, to obtain the first mixture; Described first mixture is carried out carbonization, to obtain top layer being carbon and inside is coated with the intermediate of described comprehensive silicon particle; And intermediate is carried out etching processing, remove the described silica surface of comprehensive silicon particle in described intermediate, to obtain described negative active core-shell material.
According to embodiments of the invention, the method is utilized to prepare, carbon source after carbonization forms the top layer of hollow on nano silicon particles surface, and there is space between top layer and nano silicon particles, this space is in charging, discharging electric batteries process, silicon volumetric expansion provides headspace, be conducive to keeping the structural integrity of negative active core-shell material, thus the capacity of battery is high and not easily decay, cyclicity is good, long service life.
In accordance with a further aspect of the present invention, the invention provides a kind of negative pole.According to embodiments of the invention, this negative pole comprises: aforementioned negative active core-shell material.
According to embodiments of the invention, adopt the battery of negative pole of the present invention, battery capacity is high and not easily decay, and cyclicity is good, long service life, has good high rate performance and fast charging and discharging ability.According to embodiments of the invention, battery initial specific capacities of the present invention reaches 2200mAh/g, and have reversible specific capacity to be 1200mAh/g after 80 charge and discharge cycles, capability retention can reach 54.5%.Under high magnification (4C) discharge and recharge, still there is the specific capacity (having good high rate performance and fast charging and discharging ability) higher than general commercial graphite cathode.
According to a further aspect in the invention, the invention provides a kind of battery.According to embodiments of the invention, this battery: aforesaid negative pole; Positive pole; And electrolyte.
According to embodiments of the invention, battery of the present invention, battery capacity is high and not easily decay, and cyclicity is good, long service life, has good high rate performance and fast charging and discharging ability.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 shows the displaing micro picture of negative active core-shell material according to an embodiment of the invention;
Fig. 2 shows the schematic flow sheet preparing negative active core-shell material according to an embodiment of the invention;
Fig. 3 shows the picture of CR2025 type button cell according to an embodiment of the invention;
Fig. 4 shows the charging and discharging curve schematic diagram of CR2025 type button cell 1 according to an embodiment of the invention;
Fig. 5 shows the cyclicity curve synoptic diagram of the CR2025 type button cell of Different Silicon content according to an embodiment of the invention.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Being exemplary below by the embodiment be described with reference to the drawings, only for explaining the present invention, and can not limitation of the present invention being interpreted as.
In describing the invention, term " longitudinal direction ", " transverse direction ", " on ", D score, "front", "rear", "left", "right", " vertically ", " level ", " top ", the orientation of the instruction such as " end " or position relationship be based on orientation shown in the drawings or position relationship, be only the present invention for convenience of description instead of require that the present invention with specific azimuth configuration and operation, therefore must can not be interpreted as limitation of the present invention.
Negative active core-shell material
According to an aspect of the present invention, the invention provides a kind of negative active core-shell material.With reference to figure 1, according to embodiments of the invention, this negative active core-shell material comprises: nano silicon particles and carbon base material layer, wherein, carbon base material layer is formed at least part of outer surface of nano silicon particles, further, there is space at least partially and between the outer surface of nano silicon particles in carbon base material layer.
The discovery that inventor is surprised, space is there is between the carbon base material layer of negative active core-shell material of the present invention and the outer surface of nano silicon particles, this cavity is in charging, discharging electric batteries process, silicon volumetric expansion provides headspace, be conducive to keeping the structural integrity of negative active core-shell material, thus the capacity of battery is high and not easily decay, cyclicity is good, useful life.
According to a particular embodiment of the invention, the particle diameter of nano silicon particles is 30-50nm.Thus, nano silicon particles better can discharge the stress that change in volume produces.
According to some embodiments of the present invention, the content of nano silicon particles is 35 % by weight-75 % by weight.The initial specific capacities of battery increases along with nano silicon particles content and promotes, but the content of nano silicon particles increases to a certain degree, and cycle performance can be caused to decline, inventor finds, when the content of nano silicon particles is 35 % by weight-75 % by weight, the initial specific volume of battery is high, and cyclicity is good.According to a particular embodiment of the invention, when the content of nano silicon particles is 60 % by weight, not only the initial specific volume of battery is high, and battery is after repeatedly circulating, and still has excellent cycle performance, preferably, be 60 % by weight.
According to some embodiments of the present invention, carbon base material layer obtains by SU-8 photoresist is carried out carbonization.Thus, carbon-based material has porous carbon skeleton structure, is easy to form patterned structures, lays a good foundation for realizing minicell on the sheet upper electrode arrangement of straight forming and sheet.
According to some embodiments of the present invention, carbonization is 850-950 DEG C in temperature, carries out under the condition of inert atmosphere.Thus, carbonization is effective, and the carbon-based material that carbonization is formed has good porous carbon skeleton structure, is coated on the part surface of nano silicon particles.
According to some embodiments of the present invention, described space is 10-15nm.Thus, in the size in space and charging, discharging electric batteries process, the size of nano silicon particles volumetric expansion is consistent, and be conducive to the integrality keeping negative active core-shell material structure, and the tap density of negative material is high, volume and capacity ratio is high.
Prepare the method for negative active core-shell material
According to another aspect of the invention, the invention provides a kind of method preparing negative active core-shell material.With reference to figure 2, the method is described in detail.According to embodiments of the invention, the method comprises:
The process of (a) hydrolysis oxidation
According to embodiments of the invention, be hydrolyzed nano silicon particles oxidation processes, obtains the comprehensive silicon particle with silica surface.Thus, form silicon dioxide sacrificial layer on the surface of nano silicon particles, in follow-up process, fall this silicon dioxide sacrificial layer by etching processing, thus the carbon source after nano silicon particles with the carbonization on its surface forms space as shown in Figure 2.
(b) mixed processing
According to embodiments of the invention, in described comprehensive silicon particle, add carbon source, mix, obtain the first mixture.Thus, the carbon source after carbonization can form uniform top layer at comprehensive silicon particle surface.
According to a particular embodiment of the invention, carbon source is SU-8 photoresist.Thus, after carbonization, easily formed and there is porous carbon skeleton structure, and the carbon source after carbonization easily forming patterned structures, laying a good foundation for realizing minicell on the sheet upper electrode arrangement of straight forming and sheet.
According to some embodiments of the present invention, the mass ratio of nano silicon particles and carbon source is 1:2-9.Thus, the negative active core-shell material of formation, the content of nano silicon particles is suitable, and then the initial specific volume of battery is high, and cyclicity is good.
(c) carbonization treatment
According to a particular embodiment of the invention, the first mixture is carried out carbonization, obtain top layer and be carbon and inside is coated with the intermediate of comprehensive silicon particle.Thus, through carbonization treatment, carbon source forms the porous carbon skeleton of self-supporting, is coated on the part surface of the intermediate of comprehensive silicon particle.
According to some embodiments of the present invention, described carbonization is 850-950 DEG C in temperature, carries out under the condition of inert atmosphere.Thus, carbonization is effective, and the carbon source after carbonization has good porous carbon skeleton structure, is easy to the part surface of the intermediate being coated on comprehensive silicon particle.
According to some embodiments of the present invention, described carbonization is undertaken by described first mixture is coated on silicon chip surface.Thus, the solidification of crosslinked polymer in SU-8 photoresist, microstructure is substantially fixing, forms the porous carbon skeleton of self-supporting, achieves stable support and coated to Si/SiO2 composite particles.
(d) etching processing
According to some embodiments of the present invention, intermediate is carried out etching processing, remove the silica surface of comprehensive silicon particle in intermediate, obtain negative active core-shell material.Thus, by etching processing, remove the silica surface of comprehensive silicon particle, make the carbon source formation space as illustrated in fig. 1 and 2 after the carbonization on nano silicon particles and its surface.According to some embodiments of the present invention, this space is 10-15nm.Thus, in the size in space and charging, discharging electric batteries process, the size of nano silicon particles volumetric expansion is consistent, and be conducive to the integrality keeping negative active core-shell material structure, and the tap density of negative material is high, volume and capacity ratio is high.
Negative pole and battery
In accordance with a further aspect of the present invention, the invention provides a kind of negative pole.According to embodiments of the invention, this negative pole comprises: aforementioned negative active core-shell material.
According to embodiments of the invention, adopt the battery of negative pole of the present invention, battery capacity is high and not easily decay, and cyclicity is good, long service life, has good high rate performance and fast charging and discharging ability.
According to a further aspect in the invention, the invention provides a kind of battery.According to embodiments of the invention, this battery: aforesaid negative pole; Positive pole; And electrolyte.
According to embodiments of the invention, battery of the present invention, battery capacity is high and not easily decay, and cyclicity is good, long service life, has good high rate performance and fast charging and discharging ability.
According to some embodiments of the present invention, described just very lithium disk.Thus, this positive pole as test system to electrode.
According to some embodiments of the present invention, described battery is button battery.Thus, achieve battery assembling that is simple, low cost, be convenient to carry out performance test, test result is accurate.
According to some embodiments of the present invention, described battery is half-cell.Thus, using negative pole of the present invention as work electrode, the chemical property such as charge/discharge capacity, cycle performance, coulombic efficiency, polarization potential of accurate test material.
Below with reference to specific embodiment, the present invention will be described, it should be noted that, these embodiments are only illustrative, and can not be interpreted as limitation of the present invention.
Embodiment 1
Adopt the flow process of template synthesis negative active core-shell material, as described in Figure 2, concrete grammar is as follows:
A () is by the silicon grain of 1.5g average grain diameter 30 ~ 50nm, ultrasonic disperse is in the system of 200mL ethanol and 50mL water, add 10mL28% ~ 30% ammoniacal liquor subsequently, dropwise add 13.5g tetraethoxysilane (TEOS), Keep agitation 12 hours, generates SiO in the oxidation of silicon grain surface hydrolysis
2layer, centrifugation is also repeatedly cleaned and is obtained composite particles;
B above-mentioned composite particles mixes with 13.5gSU-8 photoresist by (), be spun on silicon chip;
(c) at 900 DEG C, N
2carry out high temperature cabonization to material under environment, SU-8 photoresist becomes the porous carbon skeleton of self-supporting;
D () resulting materials immerses in 4wt%HF, 46wt% water, 50wt% ethanol system, SiO
2sacrifice layer is etched away, and obtain negative active core-shell material, the silicone content of this negative active core-shell material is 35wt%.
As shown in Figure 1, silicon grain is dispersed among carbon skeleton the displaing micro picture of negative active core-shell material prepared by said method, and carbon skeleton serves good supporting role, has the space of 10 ~ 15nm between silicon and carbon simultaneously.
According to the method described above, with the silicon grain of 1.5g average grain diameter 30 ~ 50nm and 7.3gSU-8 photoresist for the negative active core-shell material that silicone content is 50wt% prepared by raw material.
According to the method described above, with the silicon grain of 1.5g average grain diameter 30 ~ 50nm and 4.9gSU-8 photoresist for the negative active core-shell material that silicone content is 60wt% prepared by raw material.
According to the method described above, with the silicon grain of 1.5g average grain diameter 30 ~ 50nm and 2.4gSU-8 photoresist for the negative active core-shell material that silicone content is 75wt% prepared by raw material.
Embodiment 2
The negative active core-shell material utilizing embodiment 1 to prepare prepares button-shaped half-cell, and concrete processing method is as follows:
(1) negative active core-shell material of silicone content 35% prepared by the embodiment 1 of getting 4g is as active material, 0.5gSuperP is as conductive agent, 0.5g carboxymethyl cellulose (CMC), as binding agent, is coated on after being uniformly dispersed on Copper Foil, puts into 80 DEG C of vacuum drying oven dried overnight.
(2) product step (1) obtained is at 100kg/cm
2under strike out sheet.
(3) product in blocks for step (2) punching press is assembled in glove box CR2025 type button cell 1 as shown in Figure 3, wherein above-mentioned material is as negative pole, lithium disk as positive pole, Celgard film as barrier film, 1mol/LLiPF
6with EC:DEC:DMC (volume ratio 1:1:1) mixed solution as electrolyte.
As stated above, the silicone content prepared with embodiment 1 is respectively respectively the negative active core-shell material of 50wt%, 60wt% and 75wt% for active material, preparation CR2025 type button cell 2, CR2025 type button cell 3 and CR2025 type button cell 4.
Embodiment 3
CR2025 type button cell embodiment 2 obtained carries out electro-chemical test in charging and discharging lithium battery system.
1, charge-discharge test
The silicone content that embodiment 2 is obtained be 35% button cell 1 carry out charge-discharge test, specific as follows:
(1) method of testing
Under room temperature, button cell 1 is tested on battery testing system (new Weir company, CT-3008W type).
Before test, need battery to be shelved ageing 24 hours, make electrolyte fully infiltrate electrode material.
Charge cutoff voltage is set to 1.2V, and discharge cut-off voltage is set to 0.01V.
First three cycle carries out discharge and recharge with less 0.1C multiplying power (electric current 0.2mA), and subsequent cycle, by current boost 3 times, carries out discharge and recharge with the electric current of the multiplying power of 0.3C and 0.6mA, altogether carries out 30 charge and discharge cycles tests.Each charge/discharge terminates, all arrange 2 hours shelve the time.
According to discharge and recharge time, electric current and material uploading quality, the relation of actual charge/discharge specific capacity and voltage can be obtained.
(2) test result
As shown in Figure 4, when silicone content 35%, theoretical specific capacity is 1470mAh/g to the constant current charge-discharge curve of lithium ion half-cell.Can find out, actual initial specific capacities can reach 1200mAh/g, and in 1 ~ 10 cyclic process, capacity attenuation is very little, after 30 circulations, has the capability retention of 71%.In addition, also there is the comparatively long discharge platform lower than 0.3V.Result shows, utilizes lithium ion half-cell prepared by the negative active core-shell material of this method, and greatly and not easily decay, circulating battery is good for battery capacity.The initial specific capacities of this battery is more than 3 times of general commercial graphite cathode material (350mAh/g), still exceeds its about 2 times after 30 circulations.
2, cyclicity experiment
The CR2025 type button cell 1 (silicone content 35wt%) embodiment 2 prepared, CR2025 type button cell 2 (silicone content 50wt%), CR2025 type button cell 3 (silicone content 60wt%) and CR2025 type button cell 4 (silicone content 75wt%) carry out cycle performance detection, compare the impact of silicone content on circulating battery.
(1) method of testing
Under room temperature, respectively each CR2025 type button cell is tested on battery testing system (new Weir company, CT-3008W type).
Before test, need battery to be shelved ageing 24 hours, make electrolyte fully infiltrate electrode material.
Charge cutoff voltage is set to 1.2V, and discharge cut-off voltage is set to 0.01V.
First three cycle carries out discharge and recharge with less 0.1C multiplying power (electric current 0.2mA), and subsequent cycle, by current boost 3 times, carries out discharge and recharge with the electric current of the multiplying power of 0.3C and 0.6mA, altogether carries out 80 charge and discharge cycles tests.Each charge/discharge terminates, all arrange 2 hours shelve the time.
(2) test result
The cycle performance test result of each CR2025 type button cell as shown in Figure 5, the initial specific capacities of battery increases along with silicone content and promotes, but repeatedly after circulation, the sample of 60wt% silicone content has best cycle performance, namely after 80 circulations, battery capacity is 1240mAh/g.In addition, silicone content increases to a certain degree, and cycle performance can be caused to decline, and therefore, exist to trade off between lifting specific capacity and lifting cycle performance and consider, preferably, the composite material of 60wt% silicone content illustrates more excellent combination property.
In the description of this specification, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (10)
1. a negative active core-shell material, is characterized in that, comprising:
Nano silicon particles; And
Carbon base material layer, described carbon base material layer is formed at least part of outer surface of described nano silicon particles,
Wherein,
Described carbon base material layer there is space at least partially and between the outer surface of described nano silicon particles.
2. negative active core-shell material according to claim 1, is characterized in that, the particle diameter of described nano silicon particles is 30-50nm,
Optionally, the content of described nano silicon particles is 35 % by weight-75 % by weight, preferably, is 60 % by weight.
3. negative active core-shell material according to claim 1, is characterized in that, described carbon base material layer obtains by SU-8 photoresist is carried out carbonization,
Optionally, described carbonization is 850-950 DEG C in temperature, carries out under the condition of inert atmosphere.
4. negative active core-shell material according to claim 1, is characterized in that, described space is 10-15nm.
5. prepare a method for negative active core-shell material, it is characterized in that, comprising:
Be hydrolyzed nano silicon particles oxidation processes, to obtain the comprehensive silicon particle with silica surface;
Described comprehensive silicon particle is mixed with carbon source, to obtain the first mixture;
Described first mixture is carried out carbonization, to obtain top layer being carbon and inside is coated with the intermediate of described comprehensive silicon particle; And
Intermediate is carried out etching processing, removes the described silica surface of comprehensive silicon particle in described intermediate, to obtain described negative active core-shell material.
6. method according to claim 5, is characterized in that, described carbon source is SU-8 photoresist.
7. method according to claim 5, is characterized in that, the mass ratio of described nano silicon particles and described carbon source is 1:(2-9),
Optionally, described carbonization is 850-950 DEG C in temperature, carries out under the condition of inert atmosphere,
Optionally, described carbonization is undertaken by described first mixture is coated on silicon chip surface.
8. a negative pole, is characterized in that, comprising: negative active core-shell material described in any one of claim 1-4.
9. a battery, is characterized in that, comprising:
Negative pole according to claim 8;
Positive pole; And
Electrolyte.
10. battery according to claim 9, is characterized in that, described just very lithium disk,
Optionally, described battery is button battery,
Optionally, described battery is half-cell.
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| CN105514381A (en) * | 2015-12-25 | 2016-04-20 | 苏州格瑞动力电源科技有限公司 | Method for treating silicon negative materials of lithium ion battery |
| CN107946570A (en) * | 2017-11-20 | 2018-04-20 | 清华大学 | Shelly texture silicon-carbon composite electrode material |
| CN107959013A (en) * | 2017-11-20 | 2018-04-24 | 清华大学 | The carbon-silicon composite material of graphene coated silicon grain and its preparation and application |
| CN109192973A (en) * | 2018-10-30 | 2019-01-11 | 合肥国轩高科动力能源有限公司 | A kind of composite material and preparation method and application of silico-carbo core-shell structure |
| CN109411729A (en) * | 2018-10-30 | 2019-03-01 | 远东福斯特新能源有限公司 | Lithium ion battery porous silicon/carbon hollow composite material and preparation method thereof |
| CN109761239A (en) * | 2019-01-18 | 2019-05-17 | 齐鲁工业大学 | It is a kind of sensing, photoelectricity or lithium ion battery composite material and preparation method |
| CN110034285A (en) * | 2018-01-12 | 2019-07-19 | 株式会社吴羽 | Negative electrode battery material and its manufacturing method, secondary battery cathode and secondary cell |
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| CN105514381A (en) * | 2015-12-25 | 2016-04-20 | 苏州格瑞动力电源科技有限公司 | Method for treating silicon negative materials of lithium ion battery |
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| CN109192973A (en) * | 2018-10-30 | 2019-01-11 | 合肥国轩高科动力能源有限公司 | A kind of composite material and preparation method and application of silico-carbo core-shell structure |
| CN109411729A (en) * | 2018-10-30 | 2019-03-01 | 远东福斯特新能源有限公司 | Lithium ion battery porous silicon/carbon hollow composite material and preparation method thereof |
| CN109192973B (en) * | 2018-10-30 | 2021-04-16 | 合肥国轩高科动力能源有限公司 | Composite material with silicon-carbon core-shell structure and preparation method and application thereof |
| CN109761239A (en) * | 2019-01-18 | 2019-05-17 | 齐鲁工业大学 | It is a kind of sensing, photoelectricity or lithium ion battery composite material and preparation method |
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