CN104852023A - Carbon composite material and preparation method therefor - Google Patents
Carbon composite material and preparation method therefor Download PDFInfo
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- CN104852023A CN104852023A CN201510150610.4A CN201510150610A CN104852023A CN 104852023 A CN104852023 A CN 104852023A CN 201510150610 A CN201510150610 A CN 201510150610A CN 104852023 A CN104852023 A CN 104852023A
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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
- H01M4/366—Composites as layered products
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a carbon composite material and a preparation method therefor. The preparation method comprises a first step of performing oxidation treatment on graphite so as to obtain surface oxidized graphite; a second step of mixing carbohydrate, the surface oxidized graphite and a solvent so as to obtain a mixture; a third step of treating the mixture for 1-10 hours at 100-250DEG C so as to obtain a precursor; and a fourth step of calcining the precursor for 1-10 hours at 300-1600DEG C in the air so as to obtain the carbon composite material. The prepared carbon composite material has a uniform wrapping layer and a smooth surface, is wrapped completely, has a perfect appearance, and particularly has excellent electrochemical performance. The method is simple to operate and is easy to realize.
Description
Technical field
The present invention relates to a kind of preparation method of carbon composite and the carbon composite of preparation thereof.
Background technology
The development of the mankind invariably accompanies the innovation of various new technology and the application of new forms of energy, as universal along with steam engine of the first time industrial revolution; Second industrial revolution is then the application of electric power.Society, the fossil fuels such as oil, natural gas, coal are widely used, and had more than two one-hundred-year histories, the thing followed is rise in price and the energy crisis of fossil fuel.Various fossil fuel is non-renewable energy resources in addition, and reserves are extremely limited.And also to the various toxic gas of airborne release and dust while the combusts fossil energy, the acid rain caused, haze, greenhouse effect etc. have had a strong impact on life and the health of people.In addition, the energetic of electronic product and portability, as the universal of the electronic product such as laptop computer and mobile phone is also badly in need of a kind of high-energy-density and light energy source.Various reasons forces people to start to be conceived to the exploitation of new new cleaning fuel and new energy storage device.This also creates showing one's talent of lithium ion battery.
Relative to other secondary cell, the portability of lithium ion battery and high-energy-density made it in the past twenty years in led portable battery market.Now, the power resources of lithium ion battery as hybrid vehicles, the plug-in hybrid vehicles and electric vehicle are being put forth effort in the research of lithium ion battery, and lithium ion battery technology has been considered to the secondary regenerative resource that can compare favourably with wind energy, tidal energy.Lithium ion battery technology large-scale application compares in those project relying on low cost, high security, high cycle life, discharge and recharge ratio and the high-energy-density energy, and lithium ion battery technology itself also quite relies on the performance of battery material.Although scientific workers have dropped into a large amount of energy and times at the positive and negative pole material of lithium ion battery, a small amount of scientific research crystallization has wherein been only had really to achieve suitability for industrialized production.
Negative material can be divided into non-carbon negative material and carbon based negative electrodes material usually, certainly also has some scholars to be divided into: sandwich type material, ion conversion hysteria material and alloy-type material.The microstructure of negative material, quality, degree of crystallinity and form directly affect itself chemical property.Compared to positive electrode, negative material needs the capacity of larger physical dimension and Geng Gao, could realize the high-energy-density of battery like this.What larger specific area improve active material can contact area, and reduces lithium ion in the intergranular diffusion length of negative material, and in brief, less particle diameter contributes to the high-power charge-discharge performance and the capacity that promote battery.For this reason, we can be tested (BET) reference area to material and test by specific area.In other words, the decline of irreversible capacity be just equal to active material can the lifting of contact area.There is multiple state in Lithium-ion embeding graphite, as LixC6, LixC12, this theoretical capacity creating graphite-based negative material is considered to the illusion of 372mAh/g for a long time.And the non-carbon negative material with high theoretical capacity has opened up the visual field of people.
The more carbonaceous negative material of current research has Delanium, native graphite, MCMB (MCMB), height ratio capacity carbide, petroleum coke, thermal decomposed resins carbon, nano-carbon material etc.These carbon negative pole materials have respective pluses and minuses, as:
It is high that graphite type material has lower discharge platform, theoretical capacity high (372 mAh.g-1) and efficiency for charge-discharge, and particularly low cost and other advantages, is widely used in electrochemical active material.But because graphite type material has crystallization and the degree of orientation of height, make it that solvent molecule easily occur in the process of charging and be inserted into graphite layers altogether with lithium ion and cause peeling off of graphite linings, thus cause the reduction of the cycle performance of lithium ion battery; And graphite surface carbon atom has a large amount of unsaturated bonds, when initial charge, electrolyte can be decomposed to form SEI(solid electrolyte interface at graphite surface) film, make irreversible capacity first comparatively large, reduce the cycle efficieny of battery.Prior art is generally passed through at its Surface coating one deck organic substance, then the carbon composite obtaining the nucleocapsid structure of Surface coating one deck carbon through high temperature cabonization contacts to avoid organic solvent with the direct of graphite flake layer, avoid solvent molecule and lithium ion to insert altogether, reduce the specific area of graphite simultaneously.
Such as prior art has and open adds in the solution of the coated precursor of carbon (as polyacrylonitrile, Kynoar, phenolic resins, furfuryl alcohol resin, epoxy resin, coal tar asphalt, petroleum coke etc.) by graphite type material, mixing, wherein, solvent for use is generally benzene,toluene,xylene, ethylbenzene, benzinum, quinoline, thiophene or carbon disulfide, acetone, chloroform, oxolane, carbon tetrachloride, cyclohexane and 1-METHYLPYRROLIDONE etc., add heat abstraction solvent, under inert atmosphere or vacuum condition, carbonization obtains carbon coated material afterwards.The shell of the carbon composite that these class methods obtain is generally soft carbon or covered effect and bad hard carbon, and the cycle performance, cryogenic property, high rate during charging-discharging etc. of the carbon composite of preparation are unsatisfactory, can not meet the development of prior art.
Also useful oxidant carries out above-mentioned encapsulation steps after being oxidized graphite again, can prepare coating layer evenly, the carbon composite of the nucleocapsid structure of smooth surface and the coated one deck of Surface coating completely hard carbon, but its performance can not reach desirable, the development of present battery still can not be met.
Summary of the invention
The present invention is in order to overcome the still undesirable technical problem of the existing method preparing carbon composite, there is provided a kind of can prepare coating layer evenly, smooth surface, coated completely, pattern is perfect and can improve carbon composite simple to operate of cycle performance of battery, the method easily realized.
First object of the present invention is the preparation method in order to provide a kind of carbon composite, and step comprises: A, carry out oxidation processes to graphite, obtains surface oxidation graphite; B, by saccharide compound, surface oxidation graphite and solvent, obtain mixture; C, mixture is processed 1 ~ 10h at 100 DEG C ~ 250 DEG C, obtain precursor; D, by precursor under air, 300 ~ 1600 DEG C of calcining 1-10 hour, obtain carbon composite.
Second object of the present invention is to provide a kind of carbon composite, can be obtained by above-mentioned preparation method.
By long-term research, the present inventor finds that the coated precursor of existing carbon is (as polyacrylonitrile, Kynoar, phenolic resins, furfuryl alcohol resin, epoxy resin, coal tar asphalt, petroleum coke etc.) all can not obtain desirable coating layer, the chemical property of this carbon composite is developed limited, and it is coated surprisingly to find to adopt saccharide compound of the present invention to carry out, K cryogenic treatment 1 ~ 10h at 100 DEG C ~ 250 DEG C simultaneously, high-temperature calcination in air atmosphere again after precursor, and undesired higher inert atmosphere or vacuum condition, coating layer can be obtained even, smooth surface, completely coated, the perfect carbon composite of pattern, particularly the cycle performance of carbon composite is significantly improved.And method of the present invention is simple, easily realize, product quality and lot stability are all very high, and apparatus and process requires all lower, can significantly reduce costs, for the commercialization of product is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is the flow chart of preparation method's preferred embodiment of a kind of material with carbon element clad surface graphite oxide composite lithium ion battery cathode material of the present invention.
Fig. 2 is energy spectrum analysis spectrum (EDS) figure of surface oxidation graphite prepared by embodiments of the invention 1, can calculate the atomic percent of oxygen surface oxidation graphite from figure.
Fig. 3 is energy spectrum analysis spectrum (EDS) figure of surface oxidation graphite prepared by embodiments of the invention 4, can calculate the atomic percent of oxygen surface oxidation graphite from figure.
Fig. 4 is energy spectrum analysis spectrum (EDS) figure of surface oxidation graphite prepared by embodiments of the invention 6, can calculate the atomic percent of oxygen surface oxidation graphite from figure.
Fig. 5 is scanning electron microscopy (SEM) figure of carbon composite sample S1 prepared by embodiments of the invention 1.
Fig. 6 is transmission electron microscope (TEM) figure of carbon composite sample S1 prepared by embodiments of the invention 1.
Fig. 7 is the cycle performance resolution chart of battery sample S11 prepared by embodiments of the invention 1, and wherein, a is the coulombic efficiency curve of battery, and b is the specific capacity curve of battery.
Fig. 8 is scanning electron microscopy (SEM) figure of carbon composite sample S1 prepared by embodiments of the invention 3.
Fig. 9 is transmission electron microscope (TEM) figure of carbon composite sample S1 prepared by embodiments of the invention 3.
Figure 10 is the cycle performance resolution chart of battery sample S11 prepared by embodiments of the invention 3, and wherein, a is the coulombic efficiency curve of battery, and b is the specific capacity curve of battery.
Figure 11 is the Raman spectrum spectrogram of carbon composite sample S1 prepared by embodiments of the invention 1.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of preparation method of carbon composite, step comprises: A, carry out oxidation processes to graphite, obtains surface oxidation graphite; B, by saccharide compound, surface oxidation graphite and solvent, obtain mixture; C, mixture is processed 1 ~ 10h at 100 DEG C ~ 250 DEG C, obtain precursor; D, by precursor under air, 300 ~ 1600 DEG C of calcining 1-10 hour, obtain carbon composite.The carbon composite coating layer of preparation evenly, smooth surface, coated completely, the electrochemical performance of the perfect particularly material of pattern, and method is simple to operate, easily realizes.
Wherein, graphite in steps A can be the graphite through pre-treatment, the various pre-treatments that described pre-treatment is known to the skilled person, such as, can carry out drying process to graphite, such as graphite powder is placed in baking oven to dry 8 ~ 72 hours at 80 DEG C, to remove moisture unnecessary in graphite powder.Wherein, graphite of the present invention comprises native graphite or Delanium.Such as native graphite can select scale native graphite, spherical or potato shape native graphite, preferred spherical natural graphite.The average grain diameter of preferred graphite is 0.1 micron ~ 100 microns, more preferably 0.1 micron ~ 30 microns.
Wherein, the various solvents that solvent can be known to the skilled person, such as methyl alcohol, ethanol, water and ether.The mode of mixing can for stirring, ultrasonic, ball milling or nanometer mill, the present invention does not limit.
Calcining of the present invention is carried out in air atmosphere, and particularly preferably the gas flow of air is 10 ~ 500ml/min, can obtain the carbon composite of function admirable.
The temperature that the present invention preferably calcines further is 350 ~ 700 DEG C, and the time of calcining is 3 ~ 6h, optimizes the performance of material further.
Preferred saccharide compound is selected from one or more in monose, disaccharides or polysaccharide.Wherein, monose can be galactolipin, glucose or fructose; Disaccharides can be sucrose, lactose or maltose; Polysaccharide can be starch, cellulose, glycogen, glycoprotein, Arabic gum or deoxyribose.The preferred glucose of the present invention, maltose, sucrose or starch, cheap, stay in grade, optimizes the performance of material further.Preferably, the mass ratio of saccharide compound and surface oxidation graphite is 0.05 ~ 2:1, and the mass ratio of saccharide compound and solvent is 1:3.
Wherein, the method for oxidation processes comprises liquid phase method or vapor phase method.
Wherein, liquid phase method comprises and being contacted with Oxygen in Liquid agent by graphite, concrete can be placed in by graphite powder in Oxygen in Liquid agent, or graphite powder is scattered in the solvent of dissolved oxygen voltinism gas, as hydrogen peroxide, ozone and hypochloric acid water solution etc., the present invention is preferred, and Oxygen in Liquid agent is selected from hydrogen peroxide and/or ozone dissolved liquid, not only easy to implement, and function admirable.
Wherein, vapor phase method comprises and being contacted with oxidizing gas by graphite, and concrete can be use the gas of oxidizability to carry out oxidation processes to graphite powder, and the gas of oxidizability of the present invention refers to the atmosphere containing oxidizing gases, such as air.Vapor phase method need make gas and graphite powder react at a certain temperature, and preferred reaction conditions is temperature 200 ~ 1000 DEG C, time 1 ~ 10h.Further preferable temperature is 250 ~ 500 DEG C, time 3 ~ 5h, to optimize the pattern of carbon composite further.
Preferably, in the surface oxidation graphite that oxidation processes obtains, the atomic percent of oxygen is 5.0 ~ 15.0%, and the percentage by weight of oxygen is 7 ~ 20%, and preferably the atomic percent of oxygen is 6.5 ~ 9.0% further, the percentage by weight of oxygen is 8.5 ~ 10.0%, makes the performance of material more excellent.
The present invention is preferred, and the carbon composite of preparation also comprises alloy, and preferred steps B is by saccharide compound, surface oxidation graphite, alloy and solvent, obtains mixture.Namely alloy is mixed into when raw material mixes.Wherein, alloy can be metalic contamination or non-metallic inclusion.Metalic contamination can be one or more in the organic compound of the oxide of tin, copper, silver, aluminium, chromium, iron, titanium, manganese, nickel, cobalt and these metals, the nitride of these metals, the boride of these metals, the fluoride of these metals, the bromide of these metals, the sulfide of these metals or these metals.Non-metallic inclusion can be one or more in silicon, phosphorus, boron, nitrogen, carbon, sulphur and their compound.
The present invention also can sieve the product of final preparation, to obtain the carbon composite of required particle diameter.
A kind of embodiment that method of the present invention is concrete can consult Fig. 1, and be the flow chart of the preferred embodiment of the preparation method of carbon composite of the present invention, as shown in the figure, it comprises step:
S101, graphite powder is placed in baking oven dries 8 ~ 72 hours at 80 DEG C, to remove moisture unnecessary in graphite powder;
S102, dried graphite is carried out oxidation processes, obtain surface oxidation graphite;
S103, by saccharide compound and surface oxidation graphite, join in solvent, mix, obtain carbohydrate clad surface graphite oxide compound;
S104, by the carbohydrate clad surface graphite oxide compound after mixing at 100 DEG C ~ 250 DEG C drying 1 ~ 10h, until solvent evaporation is completely, obtain low-temperature carbonization precursor clad surface graphite oxide compound;
S105, low-temperature carbonization presoma under air atmosphere, gas flow is 10 ~ 500ml/min, 300 ~ 1600 DEG C calcining 1-10 hour, be preferably 350 ~ 700 DEG C sintering 3 ~ 6h, obtain material with carbon element clad surface graphite oxide composite lithium ion battery cathode material.
Invention also provides carbon composite prepared by above-mentioned preparation method, can as the negative active core-shell material of lithium ion battery, the electrochemical performance of material, particularly good cycle.
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
Dried 24 hours under 90 ° of C by 20g graphite powder, obtain dry graphite powder, get the dry powdered graphite of 10g and be placed in Muffle furnace, under 350 ° of C, constant temperature 5 hours, takes out for subsequent use after being cooled to normal temperature, obtains gas phase surface oxidation graphite.The atomic percent of its oxygen is 6.97%, and the percentage by weight of oxygen is that 9.08%(is obtained by FDAC S-3400N scanning electron microscope test, as shown in Figure 2).
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then the surface oxidation powdered graphite of the above-mentioned preparation of 7.5g is added, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10 h, after discharging, process 3h in 220 DEG C of baking ovens and obtain thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 350 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite sample S1.
Test the pattern of S-3400N type scanning electron microscopy to sample that sample S1 uses FDAC to produce, test result is as accompanying drawing 5.Covered effect of the present invention is good, can form even, complete, smooth coating layer at graphite surface.
Test the pattern of S-3400N type transmission electron microscope to sample that sample S1 uses FDAC to produce, test result is as accompanying drawing 6.Covered effect of the present invention is good, can form even, complete, smooth coating layer at graphite surface.
Using above-mentioned obtained carbon composite sample S1 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution is as electrolyte, assembling button cell sample S11, at Land BS9300(Wuhan gold promise electronics) program control automatic electrochemical test carries out electrochemical property test, test result is as Fig. 7.
Embodiment 2
20g graphite powder is dried 24 hours under 90 ° of C, obtain dry graphite powder, get 10g powdered graphite and be placed in beaker, add the hydrogen peroxide that 50mL concentration is 30%, under 80 ° of C, constant temperature is stirred to bone dry, taking-up is placed on the dry 6h of the inherent 80 ° of C of vacuum drying oven, obtains liquid phase surface oxidation graphite.
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then the surface oxidation powdered graphite of the above-mentioned preparation of 7.5g is added, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10 h, after discharging, process 3h in 220 DEG C of baking ovens and obtain thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 350 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite sample S2.
Using above-mentioned obtained carbon composite sample S2 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution as electrolyte, assembling button cell S22.
Embodiment 3
Dried 24 hours under 90 ° of C by 20g graphite powder, obtain dry graphite powder, get 10g powdered graphite and be placed in Muffle furnace, under 500 ° of C, constant temperature 5 hours, takes out for subsequent use after being cooled to normal temperature, obtains gas phase surface oxidation graphite.
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then 5g surface oxidation powdered graphite is added, 30ml water, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10h, after discharging, processes 3h in 220 DEG C of baking ovens and obtains thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 700 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite S3.
Adopt the method identical with embodiment 1 to record SEM to scheme as shown in Figure 8, TEM spectrogram as shown in Figure 9.
Using above-mentioned obtained carbon composite sample S3 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution is as electrolyte, assembling button cell sample S33, at Land BS9300(Wuhan gold promise electronics) program control automatic electrochemical test carries out electrochemical property test, test result is as Figure 10.
Embodiment 4
20g graphite powder is dried 24 hours under 90 ° of C, obtain dry graphite powder, get 10g powdered graphite and be placed in beaker, add the hydrogen peroxide that 100mL concentration is 30%, under 80 ° of C, constant temperature is stirred to bone dry, taking-up is placed on the dry 6h of the inherent 80 ° of C of vacuum drying oven, obtains liquid phase surface oxidation graphite.The atomic percent of its oxygen is 8.66%, and the percentage by weight of oxygen is 11.22%.(adopt the method identical with embodiment 1 to record EDS to scheme, as shown in Figure 3).
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then 5g surface oxidation powdered graphite is added, 30ml water, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10h, after discharging, processes 3h in 220 DEG C of baking ovens and obtains thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 700 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite S4.
Using above-mentioned obtained carbon composite sample S4 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution as electrolyte, assembling button cell sample S44.
Embodiment 5
20g graphite powder is dried 24 hours under 90 ° of C, obtain dry graphite powder, get 10g powdered graphite and be placed in beaker, add 100mL deionized water, 6g ozone successive reaction 5h is passed into according to per hour, after under 80 ° of C constant temperature be stirred to bone dry, take out and be placed on the dry 6h of the inherent 80 ° of C of vacuum drying oven, obtain liquid phase surface oxidation graphite.
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then 5g surface oxidation powdered graphite is added, 30ml water, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10h, after discharging, processes 3h in 220 DEG C of baking ovens and obtains thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 700 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite S5.
Using above-mentioned obtained carbon composite sample S5 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution as electrolyte, assembling button cell sample S55.
Embodiment 6
20g graphite powder is dried 24 hours under 90 ° of C, obtain dry graphite powder, get 10g powdered graphite and be placed in beaker, add 100mL deionized water, 6g ozone successive reaction 10h is passed into according to per hour, after under 80 ° of C constant temperature be stirred to bone dry, take out and be placed on the dry 6h of the inherent 80 ° of C of vacuum drying oven, obtain liquid phase surface oxidation graphite.The atomic percent of its oxygen is 7.38, and the percentage by weight of oxygen is that 9.59%(adopts the method identical with embodiment 1 to record EDS to scheme, as shown in Figure 4).
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then 5g surface oxidation powdered graphite is added, 30ml water, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10h, after discharging, processes 3h in 220 DEG C of baking ovens and obtains thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 700 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite S6.
Using above-mentioned obtained carbon composite sample S6 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution as electrolyte, assembling button cell sample S66.
Embodiment 7
20g graphite powder is dried 24 hours under 90 ° of C, obtain dry graphite powder, get 10g powdered graphite and be placed in beaker, add 100mL deionized water, 6g ozone successive reaction 10h is passed into according to per hour, after under 80 ° of C constant temperature be stirred to bone dry, take out and be placed on the dry 6h of the inherent 80 ° of C of vacuum drying oven, obtain liquid phase surface oxidation graphite.The atomic percent of its oxygen is 7.59, and the percentage by weight of oxygen is that 9.86%(adopts the method identical with embodiment 1 to record EDS to scheme, as shown in Figure 4).
20g glucose is stirred 12 hours with 100mL water at normal temperatures, form uniform glucose solution, then 5g surface oxidation powdered graphite is added, 30ml water, 0.5g cobalt oxide, adopt planetary ball mill milled sample, ratio of grinding media to material is 15:1, rotating speed 400rad/min, ball milling 10h, after discharging, process 3h in 220 DEG C of baking ovens and obtain thermal oxidation precursor.By thermal oxidation precursor as in porcelain boat, under air atmosphere, gas flow is 250ml/min, and selective temperature is 700 DEG C of calcinings, and temperature retention time is 6 h, is then cooled to room temperature, obtains carbon composite S7.
Using above-mentioned obtained carbon composite sample S7 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution as electrolyte, assembling button cell sample S77.
Comparative example 1
Be 215 DEG C of average grain diameters by softening point be 50 μm of petroleum asphalt powder 2g, be dissolved in No. 6 solvent naphthas of 200mL, make it dissolve completely.Under stirring, slowly add the spheroidal natural graphite that 100g average grain diameter is 17.58 μm, mix.Continue stirring and make solvent evaporates, dry under normal temperature state, obtain the homogeneous mixture of pitch and graphite.Mixture is placed in the GFG-5 HighefficientFluidbeddrier of Changzhou Chang Hong drying equipment Co., Ltd, at air atmosphere, under 270 DEG C of stirrings, is oxidized 3 hours, obtain just coating.The first coating obtained is placed in tube furnace, in a nitrogen atmosphere, is warming up to 1000 DEG C of maintenances with the heating rate of 3 DEG C/min and carries out carbonization in 1 hour, treat that temperature is down to less than 100 DEG C, take out, get carbon composite sample DS1 with 600 mesh sieves.
Using above-mentioned obtained carbon composite sample DS1 as negative active core-shell material, according to active material: acetylene black: the ratio (mass percent) that binding agent equals 80:10:10 is mixed and made into electrode slice, using lithium sheet as positive pole, using Cellgard2300 perforated membrane as barrier film, LiPF6+DMC(volume ratio 1:1 using 1mol/L) mixed solution as electrolyte, assembling button cell sample DS11.
Performance test
Loop test: at Land BS9300(Wuhan gold promise electronics) battery sample S11-S77 and DS11 that embodiment 1-7 and comparative example 1 are prepared by program control automatic electrochemical test be in MHU-1500A, after 2 hours, circulate between 2.0 ~ 3.8V with the electric current of 0.3C, the capability retention of 50 times of circulating is as shown in table 1.
Table 1
| S11 | S22 | S33 | S44 | S55 | S66 | S77 | DS11 | |
| Cycle-index | 95% | 98% | 97% | 98% | 98% | 98% | 98% | 90% |
As can be seen from above the coating layer of carbon composite prepared of the present invention evenly, smooth surface, coated completely, pattern is perfect, uses the cycle performance of the battery of carbon composite of the present invention excellent.Method of the present invention is simple simultaneously, and easily realize, product quality and lot stability are all very high, and apparatus and process requires all lower, can significantly reduce costs, for the commercialization of product is laid a good foundation.
Claims (10)
1. a preparation method for carbon composite, is characterized in that, step comprises:
A, oxidation processes is carried out to graphite, obtain surface oxidation graphite;
B, by saccharide compound, surface oxidation graphite and solvent, obtain mixture;
C, mixture is processed 1 ~ 10h at 100 DEG C ~ 250 DEG C, obtain precursor;
D, by precursor under air, 300 ~ 1600 DEG C of calcining 1-10 hour, obtain carbon composite.
2. the preparation method of carbon composite according to claim 1, is characterized in that, the gas flow of described air is 10 ~ 500ml/min.
3. the preparation method of carbon composite according to claim 1, is characterized in that, the temperature of described calcining is 350 ~ 700 DEG C, and the time of calcining is 3 ~ 6h.
4. the preparation method of carbon composite according to claim 1, is characterized in that, described saccharide compound is selected from one or more in monose, disaccharides or polysaccharide;
The mass ratio of described saccharide compound and surface oxidation graphite is 0.05 ~ 2:1, and the mass ratio of saccharide compound and solvent is 1:3.
5. the preparation method of carbon composite according to claim 1, is characterized in that, the method for described oxidation processes comprises liquid phase method or vapor phase method.
6. the preparation method of carbon composite according to claim 1, is characterized in that, described liquid phase method comprises and being contacted with Oxygen in Liquid agent by graphite, and described Oxygen in Liquid agent is selected from hydrogen peroxide and/or ozone dissolved liquid.
7. the preparation method of carbon composite according to claim 1, is characterized in that, described vapor phase method comprises and being contacted with oxidizing gas by graphite, and the reaction condition of described vapor phase method is temperature 200 ~ 1000 DEG C, time 1 ~ 10h.
8. the preparation method of carbon composite according to claim 1, is characterized in that, in described surface oxidation graphite, the atomic percent of oxygen is 5.0 ~ 15.0%, and the percentage by weight of oxygen is 7 ~ 20%.
9. the preparation method of carbon composite according to claim 1, is characterized in that, described step B is by saccharide compound, surface oxidation graphite, alloy and solvent, obtains mixture; Described alloy is selected from tin, copper, silver, aluminium, chromium, iron, titanium, manganese, nickel, cobalt and their oxide, their nitride, their boride, their fluoride, one or more in their bromide, their sulfide or their organic compound; Or one or more being selected from silicon, phosphorus, boron, nitrogen, carbon, sulphur and their compound.
10. a carbon composite, is characterized in that, described carbon composite is obtained by the preparation method of the carbon composite described in claim 1-9 any one.
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