CN103413922A - Lithium ion battery negative electrode material and preparation method thereof - Google Patents
Lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 94
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 42
- 239000010703 silicon Substances 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 82
- 239000010406 cathode material Substances 0.000 claims description 57
- 239000011261 inert gas Substances 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011164 primary particle Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011856 silicon-based particle Substances 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 239000005543 nano-size silicon particle Substances 0.000 description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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
Abstract
The invention provides a lithium ion battery negative electrode material and a preparation method thereof. The negative electrode material comprises a silicon negative electrode material SiOx with 20-100nm primary particles and a specific surface area of 50-170m<2>/g, wherein 0<x<0.1. The preparation method comprises the steps that: silicon monoxide is subjected to a reaction under a constant temperature of 800-1100 DEG C in an inert atmosphere; when the reaction is finished, the product is cooled to room temperature, and is subjected to impurity removing by using acid or alkali; the product is washed and dried, such that silicon particles are obtained; the silicon particles are subjected to carbon cladding under an inert atmosphere, and is cooled to room temperature. The lithium ion battery negative electrode material provided by the invention has high discharge capacity and circulation performance, and high stability. As a result of experiments, first discharge capacity of the lithium ion battery negative electrode material can be 2050mAh/g.
Description
Technical field
The invention belongs to technical field of new energies, relate to the energy storage electrode material, relate in particular to a kind of lithium ion battery cathode material and its preparation method.
Background technology
The main composition material of lithium ion battery comprises electrolyte, isolated material, positive and negative pole material etc.Negative material occupies larger proportion, because the performance of negative material directly affects the performance of lithium ion battery, its cost also directly determines battery cost height.The negative material of commercialization at present such as graphite, hard carbon, lithium titanate etc.Because the graphite material theoretical capacity is low, the factor such as, heavy-current discharge performance poor ground high to the electrolyte selectivity, people strive to find the material that can substitute it.Now, the lithium titanate material that cyclicity is outstanding, also have more high power capacity hard carbon material to receive concern., the lithium titanate capacity is low, voltage platform is high, therefore one-sidely all is difficult to really substitute graphite material.On the other hand, compare with graphite material, although hard carbon material has to a certain degree improved capacity, its fail safe and the expensive bottleneck that remains the limiting material application.Therefore, added the exploitation to new material beyond above-mentioned material, wherein the high power capacity silicium cathode is to have potentiality most to be applied to one of Novel anode material of power vehicle.
Energy density is large although the silicium cathode material has, production cost is suitable with graphite cathode, do not have material with carbon element obvious to environmental sensibility, have the fast charging and discharging ability and prevent the advantage such as solvent insertion, but Si also exists the problems such as the cyclical stability of material is poor as electrode material.This is mainly that change in volume causes greatly the silicon grain efflorescence owing to discharging and recharging, and poorly conductive causes.Many researchers adopts the means of ball milling to carry out the chemical property that carbon coats to improve material, by preparation Si/C composite material, improve electric conductivity, it is unusual effective method that this simple carbon coats improving the silicon carbon material electric conductivity, but the increase along with coating content, the specific capacity of silicon can sharply descend, and coats inhomogeneous.
For example, negative active core-shell material of No. 200810005625.1, Chinese patent and preparation method thereof and contain the negative pole of this material and lithium battery in the negative active core-shell material based on silica is disclosed, this active material comprises by general formula SiO
XThe silica meaned, wherein 0<x<0.8.This preparation method's more complicated, and in preparation process, use the lithium metal, there is safety problem.
The disclosed composite anode active material based on silica that comprises amorphous silicon oxide in No. 200810001626.9 patent, this amorphous silicon oxide is by SiO
XMean, 0<x<2 wherein, by the X-ray photoelectron spectroscopy measurement have 103-106ev in conjunction with can and half width (FWHE) be the silicon peak of 1.6-2.4, wherein from the calculating of the area at this silicon peak, this amorphous silicon oxide has and is more than or equal to 8% Si atomic percentage; This amorphous silicon oxide is by being included in the method for sintering hydrogen silsesquioxane preparation at the temperature of 900-1300 ℃ in inert atmosphere.The SiO that this technical scheme prepares
XIn, oxygen content is too high, has the low poor shortcoming of cyclicity that reaches of the first effect of battery.
No. 201080039819.9 disclosed negative electrode active material for lithium rechargeable battery of patent with SiO
xShown pulverous Si oxide, use possesses sealed-in type light source as light source, while as the X-ray diffraction device of the fast detector of detector, measuring, 20 °≤2 θ≤40 °, locate to detect the rake peak, the strongest line position at quartz detects peak, the height P2 at the peak of strong line position of the height P1 at above-mentioned rake peak and above-mentioned quartz meets P2/P1≤0.05, wherein preferred 0.7<x<1.5.This technology is by pulverizing SiO
XTo a certain degree improved battery performance, but the method still exists oxygen content high, cause the low poor deficiency of cyclicity that reaches of the first effect of battery.
In view of above-mentioned, have the cell negative electrode material of higher chemical property and cheaply the preparation method be the further direction of research.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery cathode material and its preparation method, lithium ion battery negative material provided by the invention has higher chemical property, and low-cost and simple preparation method is provided simultaneously.
Above-mentioned lithium ion battery negative material, comprise have primary particle 20 ~ 100nm, specific area 50 ~ 170m
2The silicium cathode material that/g forms; The chemical formulation of described silicium cathode material is SiO
x, wherein, 0<x<0.1.
Preferably: 0.01≤x≤0.09; The particle size of described silicium cathode material is controlled at 20 ~ 100nm.
The silicium cathode material preparation method of above-mentioned lithium ion battery negative material comprises the following steps:
Silicon monoxide is put in reactor, passes into inert gas, described reactor is warmed up to 800 ℃ ~ 1100 ℃, and thermostatic control 3 h ~ 10 h, fully react;
React complete, be cooled to room temperature, through acid or alkali treatment, the washing drying obtains silicon grain;
The above-mentioned silicon grain that makes is put into to reactor, pass into carbon-source gas and carry out the carbon coating under the temperature conditions of 300 ℃ ~ 1000 ℃, be cooled to room temperature and obtain the silicium cathode material that carbon coats, the particle diameter of this silicium cathode material is that 20 ~ 100nm, specific area are 50 ~ 170m
2/ g.
The speed that described reactor heats up is 1 ~ 10 ℃/min.Described acid is hydrofluoric acid.Described alkali is NaOH.The flow of described carbon-source gas is 1g/min ~ 20g/min.The described carbon coating reaction time is 0.1h ~ 1h.
Beneficial effect:
Lithium ion battery negative material provided by the invention has nanometer primary particle and high-specific surface area, and described material has nano particle, has shortened the evolving path of lithium ion in silicon grain; Material has high-specific surface area simultaneously, thereby enlarged contacting and wetted area of negative material and electrolyte, make the de-embedding of lithium ion and transmit rapider, described carbon coating means make combining closely of silicon and conductive carbon layer, and with the battery conductive agent, mix more fully with even, improved the conductance of negative material, thereby made lithium ion battery negative material provided by the invention have higher discharge capacity and cycle performance, made it have higher stability.Experimental result shows, the discharge capacity first of lithium ion battery negative material provided by the invention can reach 2050 mAh/g.
The accompanying drawing explanation
Fig. 1 is the SEM photo of the negative material that obtains of the embodiment of the present invention 1;
Fig. 2 is the TEM photo of the negative material that obtains of the embodiment of the present invention 1;
Fig. 3 is the chemical property of the negative material that obtains of the embodiment of the present invention 1.
Embodiment
Lithium ion battery negative material of the present invention comprises and has primary particle 20 ~ 100nm that specific area is 50 ~ 170m
2The silicium cathode material that/g forms; This silicium cathode material has chemical formula shown in formula (I):
SiO
x（I）；
Wherein, 0<x<0.1.
Preferably, 0.01≤x≤0.09;
Preferably, the particle size of described silicium cathode material is less than 100 nm.
The silicium cathode material preparation method of lithium ion battery negative material of the present invention comprises the following steps:
Silicon monoxide is put in reactor, passes into inert gas and be warmed up to 800 ℃ ~ 1100 ℃ with the speed of 1 ~ 10 ℃/min, control reaction temperature at 800 ℃ ~ 1100 ℃, constant temperature 3 h ~ 10 h, make fully to react in reactor;
After completion of the reaction, be cooled to room temperature, be transferred in container, then use acid or alkali treatment, obtain silicon grain through the washing drying;
Above-mentioned silicon grain is put into to reactor again, the carbon-source gas that passes into flow and be 1g/min ~ 20g/min carries out the carbon coating under the temperature conditions of 300 ℃ ~ 1000 ℃, carbon coating reaction time 0.1h ~ 1h, carbon coats and finishes to be cooled to the silicium cathode material that room temperature obtains the carbon coating, and the particle diameter of this silicium cathode material is that 20 ~ 100nm, specific area are 50 ~ 170m
2/ g.
Preferably, hydrofluoric acid is selected in acid, and alkali selects NaOH; Carbon-source gas comprises methane, acetylene etc.
The present invention forms the sign with pattern to the lithium ion battery negative material obtained, and detailed process is as follows:
The model that the present invention adopts HIT to produce is that field emission scanning electron microscope (SEM) and the Technai F20 transmission electron microscope (TEM) of S-4800 carries out the sign of pattern to lithium ion battery negative material provided by the invention, result shows, the primary particle size that negative material provided by the invention is is the 50nm left and right;
The model that the present invention adopts U.S. Merck & Co., Inc to produce is that the specific surface measuring and analysing meter of ASAP-2020M characterizes lithium ion battery negative material provided by the invention, and result shows that the specific area of negative material provided by the invention can reach 140m
2/ g.
The negative material combination that the present invention will obtain obtains lithium ion battery, has investigated the electric property of the negative material obtained, and detailed process is as follows:
Lithium ion battery negative material provided by the invention is mixed with acetylene black conductor and the binding agent mass ratio by 80:10:10 respectively, the mixture obtained is applied on the Copper Foil collector, with sheet-punching machine, make the electrode slice that diameter is 1cm after 80 ℃ of oven dry; Using the electrode slice that obtains as negative pole, to metal lithium sheet very, barrier film is Celgard 2400, and electrolyte solution is that the EC, the EMC molar concentration that contain 7%FEC are 1mol/L LiPF
6Mixed solution, the model of producing in German Braun company is the inert atmosphere glove box (O of UNlab
2And H
2The content of O all is less than 1ppm) in assembling obtain CR2032 button half-cell;
The model that the present invention adopts Wuhan Lan Dian company to produce is that the battery test system of CT 2001A carries out electrochemical property test to the CR2032 button half-cell that the present invention obtains, the voltage range of test condition is 0.01 ~ 1.5V, result shows, negative material provided by the invention is under the electric current of room temperature 400mA/g, and first discharge specific capacity reaches 2050 mAh/g.
In order to further illustrate the present invention, below in conjunction with embodiment, lithium ion battery cathode material and its preparation method provided by the invention is described in detail, but they can not be interpreted as to the restriction to protection range of the present invention.
Embodiment 1
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 5 ℃/min programming rate to 900 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 6 hours, sample is transferred in container, uses hydrofluoric acid treatment 5h, the drier silicon grain that obtains nano silicon material of washing;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 500 ℃ as the speed of 5 ℃/min, the acetylene gas that passes into flow again and be 10g/min carries out the carbon coating to this silicium cathode material, after constant temperature 0.5h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The material that embodiment 1 is prepared to gained has carried out the sign of some structures and character, as shown in the SEM and TEM photo of Fig. 1 and Fig. 2, detects through XRD, and main diffraction maximum is the characteristic diffraction peak of Si, then by XPS, determines the content of oxygen element.Primary particle is about 30nm, and specific area is 139m
2/ g.
As shown in Figure 3, the charging and discharging curve figure for the silicium cathode material of the present embodiment can find out that the specific discharge capacity of the nano material of the present embodiment under the electric current of room temperature 400mA/g is 2050mAh/g.And it has showed superior cycle performance, the capacity that even still maintains after 100 weeks is at 1520mAh/g.
Embodiment 2
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 1 ℃/min programming rate to 800 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 10 hours, sample is transferred in container, uses naoh treatment 3h, the drier silicon grain that obtains nano silicon material of washing;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 300 ℃ as the speed of 2 ℃/min, the acetylene gas that passes into flow again and be 10g/min carries out the carbon coating to this silicium cathode material, after constant temperature 1h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 20nm, and specific area is 42m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1850mAh/g, and the capacity that still maintains after 100 weeks is at 1380mAh/g.
Embodiment 3
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 3 ℃/min programming rate to 850 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 8 hours, sample is transferred in container, uses hydrofluoric acid treatment 4h, the drier silicon grain that obtains nano silicon material of washing;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 800 ℃ as the speed of 8 ℃/min, the acetylene gas that passes into flow again and be 20g/min carries out the carbon coating to this silicium cathode material, after constant temperature 0.1h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 25nm, and specific area is 39m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 2010mAh/g, and the capacity that still maintains after 100 weeks is at 1410mAh/g.
Embodiment 4
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 5 ℃/min programming rate to 950 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 6 hours, sample is transferred in container, uses hydrofluoric acid treatment, the dry silicon grain that obtains nano silicon material of washing after 5h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 800 ℃ as the speed of 4 ℃/min, the methane gas that passes into flow again and be 10g/min carries out the carbon coating to this silicium cathode material, after constant temperature 0.6h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 35nm, and specific area is 32m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 2030mAh/g, and the capacity that still maintains after 100 weeks is at 1440 mAh/g.
Embodiment 5
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 10 ℃/min programming rate to 1000 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 6 hours, sample is transferred in container, use naoh treatment, the dry silicon grain that obtains nano silicon material of washing after 5h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 900 ℃ as the speed of 9 ℃/min, the acetylene gas that passes into flow again and be 10g/min carries out the carbon coating to this silicium cathode material, after constant temperature 0.5h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 50nm, and specific area is 29m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1980mAh/g, and the capacity that still maintains after 100 weeks is at 1400 mAh/g.
Embodiment 6
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 10 ℃/min programming rate to 1100 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 4 hours, sample is transferred in container, with the dry silicon grain that obtains nano silicon material of washing after hydrofluoric acid treatment 5h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 1000 ℃ as the speed of 10 ℃/min, the methane gas that passes into flow again and be 20g/min carries out the carbon coating to this silicium cathode material, after constant temperature 0.5h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 60nm, and specific area is 23m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1900mAh/g, and the capacity that still maintains after 100 weeks is at 1460mAh/g.
Embodiment 7
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 10 ℃/min programming rate to 900 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 6 hours, sample is transferred in container, with the dry silicon grain that obtains nano silicon material of washing after hydrofluoric acid treatment 2h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 900 ℃ as the speed of 10 ℃/min, the methane gas that passes into flow again and be 10g/min carries out the carbon coating to this silicium cathode material, after constant temperature 0.5h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 30nm, and specific area is 34m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1740mAh/g, and the capacity that still maintains after 100 weeks is at 1270 mAh/g.
Embodiment 8
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 5 ℃/min programming rate to 900 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 3 hours, sample is transferred in container, with the dry silicon grain that obtains nano silicon material of washing after naoh treatment 5h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 1000 ℃ as the speed of 5 ℃/min, the methane gas that passes into flow again and be 15g/min carries out the carbon coating to this silicium cathode material, after constant temperature 1h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 40nm, and specific area is 30m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1720mAh/g, and the capacity that still maintains after 100 weeks is at 1370mAh/g.
Embodiment 9
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 5 ℃/min programming rate to 800 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 4 hours, sample is transferred in container, with the dry silicon grain that obtains nano silicon material of washing after naoh treatment 5h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 1000 ℃ as the speed of 5 ℃/min, the methane gas that passes into flow again and be 1g/min carries out the carbon coating to this silicium cathode material, after constant temperature 1h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 20nm, and specific area is 30m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1970mAh/g, and the capacity that still maintains after 100 weeks is at 1370mAh/g.
Embodiment 10
By above-mentioned preparation method of the present invention, prepare lithium ion battery negative material:
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 8 ℃/min programming rate to 1100 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 6 hours, sample is transferred in container, with the dry silicon grain that obtains nano silicon material of washing after naoh treatment 2h;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 1000 ℃ as the speed of 5 ℃/min, the methane gas that passes into flow again and be 5g/min carries out the carbon coating to this silicium cathode material, after constant temperature 1h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 100nm, and specific area is 50m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1720mAh/g, and the capacity that still maintains after 100 weeks is at 1370mAh/g.
Comparative example 1
The SiO powder of 1kg is put into to reacting furnace, pass into inert gas, and with 5 ℃/min programming rate to 900 ℃, constant temperature made fully after reaction, to be cooled to room temperature in reacting furnace in 6 hours, obtained the silicon grain of nano silicon material;
Above-mentioned silicon grain is put into to reactor again, pass into inert gas, then the programming rate of take is warming up to 500 ℃ as the speed of 5 ℃/min, the methane gas that passes into flow again and be 15g/min carries out the carbon coating to this silicium cathode material, after constant temperature 1h, be cooled to room temperature, obtain the nano silicon material that carbon coats, i.e. silicium cathode material of the present invention.
The silicium cathode material of the present embodiment, primary particle is about 100nm, and specific area is 65m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1000mAh/g, and the capacity that still maintains after 100 weeks is at 240mAh/g.
Comparative example 2
The SiO powder of 1kg is put into to reactor, pass into inert gas, then the programming rate of take is warming up to 500 ℃ as the speed of 5 ℃/min, the methane gas that passes into flow again and be 15g/min carries out the carbon coating to this silicium cathode material, after constant temperature 1h, be cooled to room temperature, obtain the silicon monoxide material that carbon coats.
The silicium cathode material of the present embodiment, primary particle is about 100nm, and specific area is 30m
2/ g, the specific discharge capacity under the electric current of room temperature 400mA/g are 1400mAh/g, and the capacity that still maintains after 100 weeks is at 210mAh/g.
Embodiment 1 ~ 10 prepares the contrast of silicium cathode material and comparative example 1 ~ 2 in Table 1:
Table 1 embodiment 1 ~ 10 and comparative example 1 ~ 2 contrast
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. lithium ion battery negative material is characterized in that: described lithium ion battery negative material comprises having once grain 20nm-100nm, specific area 50 ~ 170m
2The silicium cathode material of/g; Described silicium cathode materials chemistry formula is expressed as SiO
x, wherein, 0<x<0.1.
2. lithium ion battery negative material according to claim 1, is characterized in that: 0.01≤x≤0.09.
3. lithium ion battery negative material according to claim 1, it is characterized in that: described particle size is controlled at 20 ~ 100nm.
4. the preparation method of a lithium ion battery silicon negative material comprises the following steps:
Silicon monoxide is put in reactor, passes into inert gas, described reactor is warmed up to 800 ℃ ~ 1100 ℃, and thermostatic control 3 h ~ 10 h, fully react;
React complete, be cooled to room temperature, through acid or alkali treatment, the washing drying obtains silicon grain;
The above-mentioned silicon grain that makes is put into to reactor, pass into carbon-source gas and carry out the carbon coating under the temperature conditions of 300 ℃ ~ 1000 ℃, be cooled to room temperature and obtain the silicium cathode material that carbon coats, the particle diameter of this silicium cathode material is that 20 ~ 100nm, specific area are 50 ~ 170m
2/ g.
5. the preparation method of lithium ion battery silicon negative material according to claim 4 is characterized in that: the speed that described reactor heats up is 1 ~ 10 ℃/min.
6. the preparation method of lithium ion battery silicon negative material according to claim 4, it is characterized in that: described acid is hydrofluoric acid.
7. the preparation method of lithium ion battery silicon negative material according to claim 4, it is characterized in that: described alkali is NaOH.
8. the preparation method of lithium ion battery silicon negative material according to claim 4, is characterized in that, the flow of described carbon-source gas is 1g/min ~ 20g/min.
9. the preparation method of lithium ion battery silicon negative material according to claim 4, it is characterized in that: the described carbon coating reaction time is 0.1h ~ 1h.
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