CN108199023A - The preparation method of biological silicon carbon material, biological silicon carbon material and application - Google Patents
The preparation method of biological silicon carbon material, biological silicon carbon material and application Download PDFInfo
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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
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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
- H01M10/052—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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- 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
- H01M4/38—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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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of biological silicon carbon material, biological silicon carbon material and applications.A kind of preparation method of biology silicon carbon material, includes the following steps：It is dried after impregnating rice husk 6 hours~10 hours using inorganic acid；Under the atmosphere of protective gas, the rice husk after drying process at 400 DEG C~600 DEG C is calcined and obtains within 2 hours~4 hours carbide, the protective gas is selected from least one of argon gas, nitrogen；By the carbide and magnesium powder according to mass ratio 1：0.8~1：Grinding uniformly obtains mixture after 1.2 mixing；The mixture at 600 DEG C~800 DEG C is calcined 3 hours~5 hours and obtains pre-product；Using pre-product described in acid soak 6 hours~12 hours, the acid solution was selected from least one of hydrochloric acid, sulfuric acid and nitric acid；And obtain biological silicon carbon material within 1 hour~3 hours using pre-product described in hydrofluoric acid dips.Biological silicon carbon material prepared by the preparation method of above-mentioned biology silicon carbon material can improve lithium ion battery charge/discharge capacity, cyclical stability and high rate performance.
Description
Technical field
The present invention relates to a kind of preparation method of biological silicon carbon material, biological silicon carbon material and applications.
Background technology
With social economy rapid development and population increase, people are increasing for energy demand, however, as oil,
The fossil energies such as coal, natural gas it is non-renewable, and cannot gradually meet after exploiting for a long time economy and society hair
The needs of exhibition.In addition, a large amount of greenhouse gases and toxic gas that are generated after fossil energy burning, also in the existence ring for endangering us
Border.In recent years, with the improvement of people's environmental awareness, people are higher and higher for the cry of clean energy resource, exploitation cleaning, height
Effect, energy-efficient new energy, which substitute fossil energy, becomes the hot spot that researchers pay close attention to.
As a kind of cleaning, efficient green power supply, since the advent of the world just receives significant attention lithium ion, compared to tradition
Battery, lithium ion battery has many advantages, such as that operating voltage is high, operating temperature range is wide, energy density is big, memory-less effect.
In recent years, popularizing with intelligent electronic device, lithium ion battery is obtained in mobile phone, digital camera, smartwatch etc.
To extensive use.In addition, the application for fields such as electric vehicle, new-energy automobile, aerospace and military equipments both at home and abroad
Also it expands and energetically studies and apply.Therefore, lithium ion battery becomes a current big research tendency, improves battery specific volume
Amount, circulating ratio and cyclical stability become the principal concern of Study on Li-ion batteries.
Negative material is one of critical material of lithium ion battery, and carbon material is as the earliest lithium battery studied and apply
Negative material still receives significant attention so far.Rice husk easily causes fire, while discharge a large amount of two as agricultural wastes burning
Carbonoxide aggravates greenhouse effects, therefore obtains nano-structure porous silicon to rice husk progress carbonization treatment and obtain certain research.However, system
When standby nano-structure porous silicon is as lithium ion battery negative material, the charge/discharge capacity of lithium ion battery, cyclical stability and again
Rate performance is poor.
Invention content
Based on this, it is necessary to which providing a kind of can improve lithium ion battery charge/discharge capacity, cyclical stability and high rate performance
Biological silicon carbon material preparation method, biological silicon carbon material and application.
A kind of preparation method of biology silicon carbon material, which is characterized in that include the following steps：
It is dried after impregnating rice husk 6 hours~10 hours using inorganic acid；
Under the atmosphere of protective gas, the rice husk after drying process is calcined 2 hours at 400 DEG C~600 DEG C
Obtain carbide within~4 hours；
By the carbide and magnesium powder according to mass ratio 1：0.8~1：Grinding uniformly obtains mixture after 1.2 mixing；
By the mixture, 600 DEG C~800 DEG C calcinings obtain pre- production in 3 hours~5 hours under the atmosphere of protective gas
Object；
Using 6 hours~12 hours acid solutions of pre-product described in acid soak in hydrochloric acid, sulfuric acid and nitric acid extremely
Few one kind；And
Biological silicon carbon material is obtained using pre-product described in hydrofluoric acid dips within 1 hour~3 hours；
Wherein, the protective gas is selected from least one of argon gas and nitrogen.
The preparation method of above-mentioned biology silicon carbon material, it is cheap and easy to get using rice husk as carbon source and silicon source, it is sharp again to realize resource
With reducing environmental pollution；Preparation method is easy to operate, of low cost；Itself has very in the biological silicon carbon material of preparation
Stable chemical property, wherein amorphous silicon play obvious action in terms of capacity raising, and amorphous carbon therein
Since the presence of hole plays the expansion of silicon good cushioning effect, and can provide better transmission for the lithium of lithium battery
Channel and attachment point can improve lithium ion battery charge/discharge capacity, cyclical stability and high rate performance, improve silicon biogenic opal carbon materials
The battery performance of material.
The inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid in one of the embodiments,.
A concentration of 1mol/L~3mol/L of the inorganic acid in one of the embodiments,.
The solid-to-liquid ratio of the rice husk and the inorganic acid is 2g in one of the embodiments,:200mL~3g:
300mL。。
In one of the embodiments, with the heating rate of 1 DEG C/min~5 DEG C/min by the rice husk after drying process
It is heated to 400 DEG C~600 DEG C.
In one of the embodiments, by the carbide and magnesium powder according to mass ratio 1：0.8~1：It is ground after 1.2 mixing
Mixture is obtained within 0.5 hour~1 hour, the mode of the grinding is mechanical lapping.
The mixture is heated to 600 with the heating rate of 1 DEG C/min~5 DEG C/min in one of the embodiments,
DEG C~800 DEG C.
It is dried after the use inorganic acid impregnates rice husk 6 hours~10 hours in one of the embodiments,
The step of before further include step：Make to be soaked in water rice husk 6 hours~12 hours.
The biological silicon carbon material that the preparation method of above-mentioned biological silicon carbon material obtains.
The application of above-mentioned biological silicon carbon material in the battery.
Description of the drawings
Fig. 1 is the electron scanning micrograph of biological silicon carbon material prepared by embodiment 2；
Fig. 2 is the electron scanning micrograph of carbon silica prepared by comparative example 1；
Fig. 3 is the transmission electron microscope photo of biological silicon carbon material prepared by embodiment 2；
Fig. 4 is the transmission electron microscope photo of carbon silica prepared by comparative example 1；
Fig. 5 is the electron scanning micrograph of nano-silicon prepared by comparative example 2.
Fig. 6 is the lithium ion battery 0.1Ag of biological silicon carbon material prepared using embodiment 2-1Current density under put
Electric curve graph；
Fig. 7 is the lithium ion battery 0.1Ag of biological silicon carbon material prepared using embodiment 2-1Current density under fill
Electric curve graph；
Fig. 8 is the lithium ion battery 0.1Ag of carbon silica prepared using comparative example 1-1Current density under electric discharge
Curve graph；
Fig. 9 is the lithium ion battery 0.1Ag of carbon silica prepared using comparative example 1-1Current density under charging
Curve graph；
Figure 10 is the lithium ion battery 0.1Ag of nano-silicon prepared using comparative example 2-1Current density under charging curve
Figure；
Figure 11 is the lithium ion battery 0.1Ag of nano-silicon prepared using comparative example 2-1Current density under discharge curve
Figure；
Figure 12 be using the lithium ion battery of biological silicon carbon material prepared by embodiment 2 0.1,0.2,0.5,1Ag-1Electricity
Discharge curve under current density；
Figure 13 be using the lithium ion battery of biological silicon carbon material prepared by embodiment 2 0.1,0.2,0.5,1Ag-1Electricity
Charge graph under current density.
Specific embodiment
The preparation method, biological silicon carbon material and application of biological silicon carbon material are carried out below in conjunction with specific embodiment
Further it is described in detail.
The preparation method of the biological silicon carbon material of one embodiment, includes the following steps：
Step S110, make to be soaked in water rice husk 6 hours~12 hours.
In one of the embodiments, rice husk is impregnated using deionized water.
Rice husk is crushed in one of the embodiments, the rice husk after crushing is made to be soaked in water.Preferably, powder
The grain size of rice husk after broken is 100 microns~500 microns.
The solid-to-liquid ratio of rice husk and water is 2g in one of the embodiments,:400mL~3g:600mL.
Make to be soaked in water in one of the embodiments, and be dried after rice husk.Preferably, it is dried at 60 DEG C.
Step S120, it is dried after impregnating rice husk 6 hours~10 hours using inorganic acid.
Inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid in one of the embodiments,.
A concentration of 1mol/L~3mol/L of inorganic acid in one of the embodiments,.
The solid-to-liquid ratio of rice husk and inorganic acid is 2g in one of the embodiments,:200mL~3g:300mL.
It impregnates at room temperature in one of the embodiments,.
The time impregnated in one of the embodiments, is 7 hours~8 hours.
Neutrality is washed to after impregnating rice husk 6 hours~10 hours using inorganic acid in one of the embodiments, and is done
It is dry.
It is dried by the way of drying in one of the embodiments, the temperature DEG C of drying is 50 DEG C~70 DEG C, preferably
It is constant temperature drying at 60 DEG C.
Step S130, under the atmosphere of protective gas, the rice husk after drying process is calcined 2 at 400 DEG C~600 DEG C
Hour~obtain carbide within 4 hours.
Protective gas is selected from least one of argon gas and nitrogen.Protective gas is in one of the embodiments,
Argon gas.Certainly, other gases can also, as long as ensure provide oxygen-free environment.
In the step, in oxygen-free environment, rice husk is calcined, obtains containing carbon and silica in carbide.
In one embodiment, the mass percentage of silica is 40%~50%.
The rice husk after drying process is heated with the heating rate of 1 DEG C/min~5 DEG C/min in one of the embodiments,
To 400 DEG C~600 DEG C, it is preferred that heating rate is 5 DEG C/min.
It calcines and is carried out in tube furnace in one of the embodiments,.
Step S140, carbide and magnesium powder are according to mass ratio 1：0.8~1：Grinding uniformly obtains mixture after 1.2 mixing.
The time ground in one of the embodiments, is 0.5 hour~1 hour.
The mode ground in one of the embodiments, is mechanical lapping.Mechanical lapping is specifically as follows mortar grinder, ball
Mill etc..
Carbide and the mass ratio of magnesium powder are 1 in one of the embodiments,：0.8~1：0.9.
Carbide and the mass ratio of magnesium powder are 1 in one of the embodiments,：1.1~1：1.2.
In the step, carbide can be made to be sufficiently mixed with magnesium powder by grinding and contact, make reaction in subsequent reaction
More fully.
Step S150, by mixture, 600 DEG C~800 DEG C calcinings obtain for 3 hours~5 hours under the atmosphere of protective gas
Pre-product.
Protective gas is selected from least one of argon gas and nitrogen.Protective gas is in one of the embodiments,
Argon gas.
In one of the embodiments, by mixture with the heating rate of 1 DEG C/min~5 DEG C/min be heated to 600 DEG C~
800 DEG C, it is preferred that heating rate is 5 DEG C/min.
The time calcined in one of the embodiments, is 4 hours.
It calcines and is carried out in tube furnace in one of the embodiments,.
Step S160, acid soak pre-product 6 hours~12 hours is used.
Acid solution is selected from least one of hydrochloric acid, sulfuric acid and nitric acid.Preferably hydrochloric acid, certainly, other acid solutions can also, only
The magnesia generated in previous step can be removed.
A concentration of 1mol/L~3mol/L of acid solution in one of the embodiments, preferably 2mol/L.
The solid-to-liquid ratio of pre-product and acid solution is 0.5g in one of the embodiments,:200mL~1.5g:300mL, preferably
For 1g:250mL.
Acid soak pre-product is used in one of the embodiments, 6 hours~12 hours.
Step S170, biological silicon carbon material is obtained within 1 hour~3 hours using hydrofluoric acid dips pre-product.
A concentration of 1mol/L~3mol/L of hydrofluoric acid in one of the embodiments, preferably 2mol/L.
The solid-to-liquid ratio of pre-product and hydrofluoric acid is 0.5g in one of the embodiments,:200mL~1.5g:300mL, it is excellent
It is selected as 0.5g:200mL.
Hydrofluoric acid dips pre-product is used in one of the embodiments, 2 hours.
Place is dried using washing after hydrofluoric acid dips pre-product 1 hour~3 hours in one of the embodiments,
Reason.Preferably, the mode of drying process is drying, and the temperature DEG C of drying is 50 DEG C~70 DEG C.
In the step, hydrofluoric acid removes unreacted silica.
The preparation method of above-mentioned biology silicon carbon material, it is cheap and easy to get using rice husk as carbon source and silicon source, it is sharp again to realize resource
With reducing environmental pollution；Preparation method is easy to operate, of low cost；Itself has very in the biological silicon carbon material of preparation
Stable chemical property, wherein amorphous silicon play obvious action in terms of capacity raising, and amorphous carbon therein
Since the presence of hole plays the expansion of silicon good cushioning effect, and can provide better transmission for the lithium of lithium battery
Channel and attachment point can improve lithium ion battery charge/discharge capacity, cyclical stability and high rate performance, improve silicon biogenic opal carbon materials
The battery performance of material.
The biological silicon carbon material of one embodiment is prepared by the preparation method of above-mentioned biological silicon carbon material.
The specific surface area of biological silicon carbon material is 180m in one of the embodiments,2/ g~200m2/g。
The porosity of biological silicon carbon material is 20%~40% in one of the embodiments,.
The aperture of biological silicon carbon material is 6nm~9nm in one of the embodiments,.
The mass percentage of carbon is 70%~90% in biological silicon carbon material in one of the embodiments,.
Above-mentioned negative material of the biology silicon carbon material as lithium ion battery, can improve lithium ion battery charge/discharge capacity,
Cyclical stability and high rate performance, specific discharge capacity still have the capacity of 550 every gram of milliampere hour after 200 cycles, together
When also have preferable high rate performance.
The application of above-mentioned biological silicon carbon material in the battery.
Battery is lithium ion battery in one of the embodiments,.
Negative material of the biological silicon carbon material as lithium ion battery in one of the embodiments,.
Above-mentioned biology silicon carbon material is applied to battery, can improve lithium ion battery charge/discharge capacity, cyclical stability and again
Rate performance.
It is illustrated below in conjunction with specific embodiment.
Embodiment 1
The preparation of biological silicon carbon material includes the following steps：
The rice husk of 4g is first impregnated 6 hours, then impregnate 8 at room temperature with the hydrochloric acid of 200mL1mol/L with 400mL deionized waters
Hour, 60 DEG C of dryings in an oven；
The dried rice husks of 3g are placed in tube furnace under protection of argon gas, 500 are warming up to the heating rate of 1 DEG C/min
DEG C calcining obtains carbide in 2 hours；
Carbide 0.5g with the magnesium powder of 0.5g is mixed, is ground 0.5 hour using agate mortar and obtains mixture；
Mixture is placed in tube furnace and is warming up to 700 DEG C with the heating rate of 1 DEG C/min, and keeps the temperature 3 hours and obtains and is pre-
Product；
Pre-product 0.5g is first used to the salt acid soak of 200mL1mol/L 6 hours, then the hydrofluoric acid with 200mL1mol/L
Drying is to biomass silicon carbon material at impregnating 1 hour, 50 DEG C.
Embodiment 2
The preparation of biological silicon carbon material includes the following steps：
The rice husk of 5g is first impregnated 12 hours, then soaked at room temperature with the hydrochloric acid of 300mL 3mol/L with 600mL deionized waters
Bubble 10 hours, in an oven 60 DEG C of dryings；
The dried rice husks of 4g are placed in tube furnace under protection of argon gas, 550 are warming up to the heating rate of 5 DEG C/min
DEG C, calcining obtains carbide in 2 hours；
Carbide 0.5g with the magnesium powder of 0.4g is mixed, is ground 1 hour using agate mortar and obtains mixture；
Mixture is placed in tube furnace and is warming up to 700 DEG C with the heating rate of 5 DEG C/min, and keeps the temperature 5 hours and obtains and is pre-
Product；
Pre-product 0.5g is first used to the salt acid soak of 300mL2mol/L after 12 hours, then the hydrogen fluorine with 300mL3mol/L
Drying is to biomass silicon carbon material at acid soak 1 hour, 70 DEG C.
Embodiment 3
The preparation of biological silicon carbon material includes the following steps：
The rice husk of 6g is first impregnated 8 hours, then impregnated at room temperature with the hydrochloric acid of 250mL2mol/L with 800mL deionized waters
10 hours, 60 DEG C of dryings in an oven；
The dried rice husks of 4g are placed in tube furnace under protection of argon gas, are warming up to the heating rate of 2.5 DEG C/min
600 DEG C, calcining obtains carbide in 3 hours；
Carbide 0.5g with the magnesium powder of 0.6g is mixed, is ground 40 minutes using agate mortar and obtains mixture；
Mixture is placed in tube furnace and is warming up to 650 DEG C with the heating rate of 2.5 DEG C/min, and keeps the temperature 5 hours and obtains
Pre-product；
Pre-product 0.5g is first used to the salt acid soak of 250mL1.5mol/L after 10 hours, then with 250mL1.5mol/L's
Drying is to biomass silicon carbon material at hydrofluoric acid dips 1 hour, 60 DEG C.
Embodiment 4
The preparation of biological silicon carbon material includes the following steps：
The rice husk of 6g is first impregnated 10 hours, then soaked at room temperature with the hydrochloric acid of 300mL 2mol/L with 500mL deionized waters
Bubble 10 hours, in an oven 60 DEG C of dryings；
The dried rice husks of 4g are placed in tube furnace under protection of argon gas, 600 are warming up to the heating rate of 3 DEG C/min
DEG C, calcining obtains carbide in 3 hours；
Carbide 0.5g with the magnesium powder of 0.6g is mixed, is ground 50 minutes using agate mortar and obtains mixture；
Mixture is placed in tube furnace and is warming up to 700 DEG C with the heating rate of 3 DEG C/min, heat preservation obtains pre- production in 5 hours
Object；
Pre-product 0.5g is first used to the salt acid soak of 300mL1mol/L after 12 hours, then the hydrogen fluorine with 300mL1mol/L
Drying is to biomass silicon carbon material at acid soak 1 hour, 60 DEG C.
Comparative example 1
The rice husk of 4g is first impregnated 10 hours, then soaked at room temperature with the hydrochloric acid of 300mL 2mol/L with 500mL deionized waters
Bubble 10 hours, in an oven 60 DEG C of dryings；
The dried rice husks of 4g are placed in tube furnace under protection of argon gas, 550 are warming up to the heating rate of 5 DEG C/min
DEG C, calcining obtains carbon silica in 3 hours.
Comparative example 2
The rice husk of 4g is first impregnated 10 hours, then soaked at room temperature with the hydrochloric acid of 300mL 2mol/L with 500mL deionized waters
Bubble 10 hours, in an oven 60 DEG C of dryings；
The dried rice husks of 4g are placed in tube furnace under the atmosphere of air, are warming up to the heating rate of 5 DEG C/min
550 DEG C, obtain nano silicon dioxide.
The mass mixings such as nano silicon dioxide and magnesium powder are homogeneously disposed in special sealing container, argon gas is protected in tube furnace
It under shield, is warming up to 650 DEG C with the heating rate of 5 DEG C/min and keeps the temperature 5 hours, obtained product is removed for 12 hours with salt acid soak
After washing neutral drying, unreacted silica, last deionization are removed with hydrofluoric acid dips half an hour for the impurity such as magnesia
Vacuum drying obtains nano-silicon after washing neutrality.
Please refer to Fig. 1 to Fig. 4, Fig. 1 is that the scanning electron microscope of biological silicon carbon material prepared by embodiment 2 is shone
Piece, Fig. 2 are the electron scanning micrograph of carbon silica prepared by comparative example 1, and Fig. 3 is biogenic opal prepared by embodiment 2
The transmission electron microscope photo of carbon material, Fig. 4 are the transmission electron microscope photo of carbon silica prepared by comparative example 1,
Fig. 5 is the electron scanning micrograph of nano-silicon prepared by comparative example 2.
It can be seen that carbon silica of the biological silicon carbon material compared to comparative example 1 of the preparation of embodiment 2 from Fig. 1~Fig. 4
And the nano silicon material structure of comparative example 2 becomes loose, has abundant pore structure.
By BET to the nanometer of the biological silicon carbon material of Examples 1 to 4, the carbon silica of comparative example 1 and comparative example 2
The specific surface area of silicon is tested, by BJH to the biological silicon carbon material of Examples 1 to 4, the carbon silica of comparative example 1 and
The porosity of the nano-silicon of comparative example 2 is tested, and the results are shown in Table 1.
Table 1
| Item | Specific surface area (m2/g) | Porosity |
| Embodiment 1 | 181 | 25% |
| Embodiment 2 | 198 | 36% |
| Embodiment 3 | 186 | 29% |
| Embodiment 4 | 192 | 31% |
| Comparative example 1 | 18 | 4% |
| Comparative example 2 | 118 | 15% |
The composition of biological silicon carbon material obtained using thermogravimetry testing example 1~4, the carbon dioxy of test comparison example 1
The composition of the nano-silicon of SiClx and comparative example 2 the results are shown in Table 2 (percentage composition in table 2 is mass percentage).
Table 2
| Item | Composition |
| Embodiment 1 | 86% carbon, 14% silicon |
| Embodiment 2 | 87% carbon, 13% silicon |
| Embodiment 3 | 92% carbon, 8% silicon |
| Embodiment 4 | 90% carbon, 10% silicon |
| Comparative example 1 | 61% carbon, 39% silica |
| Comparative example 2 | Silicon |
By the nano-silicon of the biological silicon carbon material of embodiment 2, the carbon silica of comparative example 1 and comparative example 2 (hereinafter referred to as
Biomaterial) applied to lithium ion battery progress charge-discharge test.
During charge-discharge test, by biomaterial and acetylene black, PVDF according to mass ratio 7:2:1 ratio is uniformly mixed to obtain
Mixture is allowed to form uniformly mixed slurry, slurry is evenly coated in then to NMP is added dropwise in mixture and stirs 6 hours
Copper foil is struck out into 12 millimeters of diameter on copper foil and after 120 DEG C of vacuum drying chamber drying 12 hours, drying using press machine
Sequin.The cathode of lithium ion battery is made with this, in the lithium ion battery applied to model CR2025 types.Wherein, type
Number lithium piece use to be used as to electrode in the lithium ion battery of CR2025 types, diaphragm PP, electrolyte is EC/DMC (volume ratios 1:
1).Charge-discharge test is carried out to lithium ion battery.
The 0.1Ag in blue electricity CT2001A multi-channel battery test systems-1It is tested under current density, final voltage model
It encloses for 0.02-3.0V, uses cycle performance figure such as Fig. 6 and Fig. 7 institutes of the lithium ion battery of the biological silicon carbon material of embodiment 2
Show, using the carbon silica of comparative example 1 lithium ion battery cycle performance figure as can be seen from figures 8 and 9.
Negative material of the biological silicon carbon material of embodiment 2 as lithium ion battery, 0.1A are can be seen that from Fig. 6 and Fig. 7
g-1Current density under after charge and discharge cycles 200 times, the capacity still with 550 every gram of milliampere hour；It can from Fig. 8 and Fig. 9
Go out, the negative material of the carbon silica of comparative example 1 as lithium ion battery, 0.1A g-1Current density under charge and discharge cycles
After 200 times, specific discharge capacity is 143 every gram of milliampere hour, and capacity significantly decreases；Just it can be seen that pair from Figure 10 and Figure 11
Negative material of the nano-silicon of ratio 2 as lithium ion battery, 0.1A g-1Current density under charge and discharge 10 enclose after, discharge ratio
Capacity is only 56 every gram of milliampere hour, and capacity is 0.1 every gram of milliampere hour after 200 circles, and capacity and stability have clearly disadvantageous.
Can be seen that from Figure 12 and Figure 13 the lithium ion battery of biological silicon carbon material prepared using embodiment 2 have compared with
Good high rate performance.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that those of ordinary skill in the art are come
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of biology silicon carbon material, which is characterized in that include the following steps：
It is dried after impregnating rice husk 6 hours~10 hours using inorganic acid；
Under the atmosphere of protective gas, it is small that the rice husk after drying process is calcined at 400 DEG C~600 DEG C to 2 hours~4
When obtain carbide；
By the carbide and magnesium powder according to mass ratio 1：0.8~1：Grinding uniformly obtains mixture after 1.2 mixing；
By the mixture, 600 DEG C~800 DEG C calcinings obtain pre-product in 3 hours~5 hours under the atmosphere of protective gas；
Using 6 hours~12 hours acid solutions of pre-product described in acid soak in hydrochloric acid, sulfuric acid and nitric acid at least one
Kind；And
Biological silicon carbon material is obtained using pre-product described in hydrofluoric acid dips within 1 hour~3 hours；
Wherein, the protective gas is selected from least one of argon gas and nitrogen.
2. the preparation method of biology silicon carbon material according to claim 1, which is characterized in that the inorganic acid is selected from salt
At least one of acid, sulfuric acid and nitric acid.
3. the preparation method of biology silicon carbon material according to claim 1, which is characterized in that the concentration of the inorganic acid
For 1mol/L~3mol/L.
4. it is according to claim 3 biology silicon carbon material preparation method, which is characterized in that the rice husk with it is described inorganic
The solid-to-liquid ratio of strong acid is 2g:200mL~3g:300mL.
5. the preparation method of biology silicon carbon material according to claim 1, which is characterized in that with 1 DEG C/min~5 DEG C/min
Heating rate the rice husk after drying process is heated to 400 DEG C~600 DEG C.
6. the preparation method of biology silicon carbon material according to claim 1, which is characterized in that by the carbide and magnesium powder
According to mass ratio 1：0.8~1：It is ground after 1.2 mixing and obtains within 0.5 hour~1 hour mixture, the mode of the grinding is machinery
Grinding.
7. it is according to claim 1 biology silicon carbon material preparation method, which is characterized in that by the mixture with 1 DEG C/
The heating rate of min~5 DEG C/min is heated to 600 DEG C~800 DEG C.
8. the preparation method of biology silicon carbon material according to claim 1, which is characterized in that use inorganic acid described
Step is further included before impregnating the step of rice husk is dried after 6 hours~10 hours：The rice husk 6 hours~12 that makes to be soaked in water is small
When.
9. the biological silicon carbon material obtained by the preparation method of claim 1~8 any one of them biology silicon carbon material.
10. the application of biological silicon carbon material in the battery described in claim 9.
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| CN110943211A (en) * | 2019-12-16 | 2020-03-31 | 安徽工业大学 | Preparation method of high-performance Si/C negative electrode material |
| CN113178564A (en) * | 2021-04-25 | 2021-07-27 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| WO2022140982A1 (en) * | 2020-12-28 | 2022-07-07 | 宁德新能源科技有限公司 | Negative electrode sheet, electrochemical device comprising negative electrode sheet, and electronic device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110112376A (en) * | 2019-03-25 | 2019-08-09 | 华南农业大学 | A kind of preparation method and application of porous oxidation Asia silicon/carbon compound cathode materials |
| CN110943211A (en) * | 2019-12-16 | 2020-03-31 | 安徽工业大学 | Preparation method of high-performance Si/C negative electrode material |
| WO2022140982A1 (en) * | 2020-12-28 | 2022-07-07 | 宁德新能源科技有限公司 | Negative electrode sheet, electrochemical device comprising negative electrode sheet, and electronic device |
| CN113178564A (en) * | 2021-04-25 | 2021-07-27 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| CN113178564B (en) * | 2021-04-25 | 2023-01-03 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
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