CN102659091A - High-capacity graphite material and preparation method as well as application thereof - Google Patents
High-capacity graphite material and preparation method as well as application thereof Download PDFInfo
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Abstract
The invention relates to a high-capacity graphite material and a preparation method as well as application thereof. The high-capacity graphite material comprises artificial graphite and natural graphite, wherein the mass ratio of artificial graphite to natural graphite is 20:1 to 1:1. According to the preparation method, the artificial graphite and the natural graphite are uniformly mixed according to a certain mass ratio, and then surface modification is carried out on the mixture. The prepared graphite material has the advantages of high discharge capacity, high first efficiency, long cycle life, low cost and the like; the discharge capacity of the high-capacity graphite material can reach up to more than 350mAh/g (even reach up to more than 368mAh/g); a half-cell of the high-capacity graphite material charges and discharges at the 1C multiple power; after the high-capacity graphite material cycles for 100 times, the capacity retention ratio of the high-capacity graphite material is still more than 90% (even reaches up to more than 96.3%); the first efficiency reaches up to more than 95.5%; and the manufacturing cost is reduced by about 1-10%. The high-capacity graphite material provided by the invention not only can meet the requirement of a lithium ion power battery for the high multiplying power charge-discharge of the material, but also reduces the manufacturing cost of the cathode material of the lithium ion battery.
Description
Technical field
The present invention relates to the lithium ion battery material field, be specifically related to a kind of graphite material and preparation method thereof and its application of heavy body.
Background technology
Since sony corporation of japan in 1991 successfully was used to carbon material to prepare lithium ion battery negative, carbon negative electrode material of lithium ion cell just received much concern.In recent years, carbon negative electrode material of lithium ion cell widespread use in various portable type electronic products and communication tool.The world today, the energy is deficient day by day, and national governments are stepping up exploitation with each big automobile enterprise does not have discharging, free of contamination electromobile.Lithium ion battery is as a kind of novel rechargeable cell, has advantages such as high-voltage, high-energy-density, environment friendly and pollution-free, memory-less effect, is described as " the most promising chemical power source ".
One of gordian technique of lithium ion battery is the selection and the research of negative material, and the quality of negative material quality directly influences the chemical property of battery.At present, the raw material of wood-charcoal material has become business-like lithium ion battery negative material.Wherein, natural graphite has higher specific storage, lower advantages such as price, but has first that irreversible capacity is big, cycle performance is relatively poor, is not suitable for defective such as high rate charge-discharge; The structural stability of synthetic graphite is high, and embedding lithium excellent property has extended cycle life, and the pole piece process industrial art performance is good, obtains certainly extensive and use in the industry, but has defectives such as price is higher, specific storage is lower.
In order to overcome the defective that natural graphite and synthetic graphite exist; Improve the chemical property of carbon negative pole material; Reduce its manufacturing cost; The researchist takes several different methods that graphite is carried out surface-treated, comprises methods such as organism coating, oxidation modification, reduction modification, the processing of physics method, doping vario-property.
CN1984841A discloses a kind of graphite material and method of manufacture thereof, and mesophasespherule through calcination processing, is mixed with the non-solution state of metallic substance; Remove dispersion agent; Adopt PVD method or CVD method to make on the outside surface of this metallic substance attached to this graphite material then,, obtain surperficial bossed graphite bead again through graphitization processing; With aspects such as the fast charging and discharging performance that improves the graphite bead, cycle performances, and improved loading capacity.But there is complex process in this method, and is wayward, has metallic element residual easily, and the projection of particle surface increases, and increases the specific surface area of particle surface, thereby increases its irreversible capacity first, and increase its production cost.
CN1417876A discloses the employing solution method at the compound a certain amount of MOX of graphite surface; Obtain graphite cathode material of MOX coating and preparation method thereof after the oven dry, the preparation technology of this method is simple, safety; Cost is low; Prepared graphite material specific storage is high, but needs to use acid-base solution and produce waste liquid, causes environmental pollution.
CN101246962A discloses and has used the perferrate liquid-phase oxidation to handle the method for natural graphite, and the preparation condition of this method is gentle, and significantly improves the reversible capacity of modified graphite, but its cycle performance still can not be met the need of market.For this reason, improve the loading capacity of negative material, the manufacturing cost that effectively reduces negative material becomes the research focus.
Summary of the invention
The object of the present invention is to provide a kind of graphite material of heavy body, said graphite material is made up of synthetic graphite and natural graphite, and wherein, the mass ratio of synthetic graphite and natural graphite is 20: 1-1: 1.
In the optimal technical scheme of the present invention; Said graphite material is made up of synthetic graphite and natural graphite; Wherein, The particle shape of said synthetic graphite and natural graphite is selected from sphere, subsphaeroidal, oval, needle-like, tabular, fibrous, lepidiod any or its combination, is preferably sphere, subglobose any or its combination.
In the optimal technical scheme of the present invention, said graphite material is made up of synthetic graphite and natural graphite, and the mass ratio of synthetic graphite and natural graphite is 15: 1-3: 1, and the mass ratio that is preferably synthetic graphite and natural graphite is 10: 1-4: 1.
In the optimal technical scheme of the present invention, said synthetic graphite is selected from any or its combination that oil is needle coke, coal-based needle coke, MCMB, hard charcoal, is preferably MCMB.
In the optimal technical scheme of the present invention, described natural graphite is selected from natural flake graphite.
In the optimal technical scheme of the present invention, the meta particle diameter (D of said synthetic graphite
50) be 1-80 μ m, be preferably 10-70 μ m, more preferably 20-50 μ m.
In the optimal technical scheme of the present invention, the D of said natural graphite
50Be 1-80 μ m, be preferably 5-60 μ m, more preferably 10-40 μ m.
In the optimal technical scheme of the present invention; The mixture of described synthetic graphite, natural graphite or synthetic graphite and natural graphite carries out surface-treated; The method of preferred said surface-treated is selected from any or its combination that reduction modification method, oxidation modification method, organism coat method, physically modified method, doping vario-property method, and the method for surface reduction modification more preferably, oxidation modification method, organism coat any or its combination of method.
In the optimal technical scheme of the present invention, said reduction modification is selected from LiAlH with reductive agent
4, NaBH
4, LiBH
4, Al (BH
4)
3, oxalic acid, Hypophosporous Acid, 50, sodium hypophosphite, Sulfothiorine, tin protochloride any or its combination.
In the optimal technical scheme of the present invention, said oxidation modification is selected from the vitriol oil, concentrated nitric acid, O with oxygenant
2, ydrogen peroxide 50, ozone, hypochlorous acid, concentrated hydrochloric acid, potassium perchlorate, potassium permanganate, iodine, bromine water any or its combination.
In the optimal technical scheme of the present invention; Said organism coating method is selected from vapour deposition and coats method, liquid phase and coat method, fusion and coat any or its combination that method, solid phase mixing coat method, is preferably solid phase mixing and coats any or its combination that method, liquid phase coat method.
In the optimal technical scheme of the present invention; The organism that uses in the said organism coating method is selected from any or its combination of mid-temperature pitch, hard pitch, secondary coal-tar pitch, petroleum pitch, coal tar, Z 150PH, styrene-butadiene rubber(SBR), CMC 99.5, PS, SE, polyacrylonitrile, resol, furfuryl resin, epoxy resin, glucose, sucrose, fructose, Hydrocerol A, Mierocrystalline cellulose, starch, is preferably any or its combination of mid-temperature pitch, resol, furfuryl resin, epoxy resin, sucrose, Hydrocerol A.
Another object of the present invention is to provide a kind of preparation method of graphite material of heavy body, it is characterized in that said graphite material is made up of synthetic graphite and natural graphite, the mass ratio of synthetic graphite and natural graphite is 20: 1-1: 1, comprise the steps:
(1) takes by weighing the synthetic graphite and the natural graphite of aequum, with its uniform mixing;
(2) synthetic graphite behind the uniform mixing and natural graphite mixture are carried out surface-treated.
In the optimal technical scheme of the present invention, the described blending means of step (1) is selected from any or its combination of ball mill mixing method, dispersion agent dispersing and mixing method, mixing machine hybrid system.
In the optimal technical scheme of the present invention; Said graphite material is made up of synthetic graphite and natural graphite; Wherein, The particle shape of said synthetic graphite and natural graphite is selected from sphere, subsphaeroidal, oval, needle-like, tabular, fibrous, lepidiod any or its combination, is preferably sphere, subglobose any or its combination.
In the optimal technical scheme of the present invention, said graphite material is made up of synthetic graphite and natural graphite, and the mass ratio of synthetic graphite and natural graphite is 15: 1-3: 1, and the mass ratio that is preferably synthetic graphite and natural graphite is 10: 1-4: 1.
In the optimal technical scheme of the present invention, said synthetic graphite is selected from any or its combination that oil is needle coke, coal-based needle coke, MCMB, hard charcoal, is preferably MCMB.
In the optimal technical scheme of the present invention, described natural graphite is selected from natural flake graphite.
In the optimal technical scheme of the present invention, the meta particle diameter (D of said synthetic graphite
50) be 1-80 μ m, be preferably 10-70 μ m, more preferably 20-50 μ m.
In the optimal technical scheme of the present invention, the D of said natural graphite
50Be 1-80 μ m, be preferably 5-60 μ m, more preferably 10-40 μ m.
In the optimal technical scheme of the present invention; The dispersion agent that uses in the described dispersion agent dispersing and mixing method is selected from any or its combination of water, methyl alcohol, ethanol, propyl alcohol, Virahol, Ucar 35, butanols, butyleneglycol, acetone, is preferably water, methyl alcohol, alcoholic acid any or its combination.
In the optimal technical scheme of the present invention, the method for removing dispersion agent or solvent in the described dispersion agent dispersing and mixing method is selected from evaporation, distillation, filtration, centrifugal, exsiccant any or its combination.
In the optimal technical scheme of the present invention; The method of said surface-treated is selected from any or its combination that reduction modification method, oxidation modification method, organism coat method, physically modified method, doping vario-property method, is preferably any or its combination that surface reduction modification method, oxidation modification method, organism coat method.
In the optimal technical scheme of the present invention, said reduction modification is selected from LiAlH with reductive agent
4, NaBH
4, LiBH
4, Al (BH
4)
3, oxalic acid, Hypophosporous Acid, 50, sodium hypophosphite, Sulfothiorine, tin protochloride any or its combination.
In the optimal technical scheme of the present invention, said oxidation modification is selected from the vitriol oil, concentrated nitric acid, O with oxygenant
2, ydrogen peroxide 50, ozone, hypochlorous acid, concentrated hydrochloric acid, potassium perchlorate, potassium permanganate, iodine, bromine water any or its combination.
In the optimal technical scheme of the present invention; Said organism coating method is selected from vapour deposition and coats method, liquid phase and coat method, fusion and coat any or its combination that method, solid phase mixing coat method, is preferably solid phase mixing and coats any or its combination that method, liquid phase coat method.
In the optimal technical scheme of the present invention; The organism that uses in the said organism coating method is selected from any or its combination of mid-temperature pitch, hard pitch, secondary coal-tar pitch, petroleum pitch, coal tar, Z 150PH, styrene-butadiene rubber(SBR), CMC 99.5, PS, SE, polyacrylonitrile, resol, furfuryl resin, epoxy resin, glucose, sucrose, fructose, Hydrocerol A, Mierocrystalline cellulose, starch, is preferably any or its combination of mid-temperature pitch, resol, furfuryl resin, epoxy resin, sucrose, Hydrocerol A.
Defectives such as the capacity that the present invention is directed to the synthetic graphite existence is low, natural graphite cycle performance difference; Synthetic graphite, natural graphite are carried out surface-treated according to certain mass after than uniform mixing; Make a kind of lithium ion battery negative material of heavy body; The negative material that makes has loading capacity height, the high and advantage such as have extended cycle life of efficient first, has satisfied the requirement of lithium-ion-power cell to the material high rate charge-discharge, and has effectively reduced the manufacturing cost of lithium ion battery negative material.
The application that another object of the present invention is to provide the graphite material of heavy body of the present invention to be used for preparing lithium ion battery.
In order clearly to explain protection scope of the present invention, the present invention defines term as follows:
Graphite mixture of the present invention is claimed the mixture of synthetic graphite and natural graphite again, and the synthetic graphite and the natural graphite uniform mixing of certain mass ratio made.
Needle coke of the present invention comprises that oil is two kinds of needle coke and coal-based needle cokes, for a kind of foreign matter content seldom, have lower resistance and thermal expansivity, and a very high easy graphitized carbon of anisotropy degree.As an example, can according to document (in spirit, Chen Laifu, " production of coal-based needle coke ", " colliery modernization " supplementary issue, 2009: the disclosed method preparation 110-111 page or leaf).
MCMB of the present invention is a kind of of synthetic graphite; Can BO, raw material such as pitch (wherein, said pitch comprises mid-temperature pitch, secondary coal-tar pitch, petroleum pitch etc.), residual oil, coal tar, secondary petroleum heavy oil, carbolineum, polycyclic aromatic hydrocarbons makes.As an example, can be according to the preparation of document patents of invention such as (, " the copolycondensation preparation method of MCMB ", 00133301.1) Wang Chengyang disclosed method.
Hard charcoal of the present invention is claimed difficult graphitized carbon again, is the RESEARCH OF PYROCARBON of high molecular polymer.The cross-linked resin that will have special construction can get hard carbon 1000 ℃ of left and right sides pyrolysis.As an example, can be according to document (Sun Hao etc., " lithium ion battery hard carbon cathode material progress ", " New Chemical Materials ", the preparation of 2005,33 (11) disclosed methods.
Meta particle diameter (D of the present invention
50) be meant that the cumulative particle sizes percentile of sample reaches 50% o'clock pairing particle diameter.The present invention adopts laser method and selects for use MASTERSIZER 2000 determinators to measure the D50 of material.
Particle diameter according to the invention detects and adopts the MASTERSIZER 2000 type laser particle analyzers of Britain Ma Erwen company to test, and refractive index is 2.6, and distilled water medium wet method is disperseed, ultrasonic-wave assisted dispersion.
Aspects such as the surface topography of the Japanese JSM-6700F scanning electron microscope observation sample of science of electronic scanning of the present invention micro-(SEM) test employing, particle size, emission voltage is 5KV, and powder surface is carried out vacuum metal spraying 2min.Wherein, Sem scans the high-power electron beam that gathering obtains on sample; Inspire various physical signallings; Comprise secondary electron, times scattered electrons, transmitted electron, absorption electronics, visible light and X ray etc., and the reception through these signals, amplify and be shown as picture and analytical sample, obtain the various information of sample topography.
Reduction modification method of the present invention is meant with reducing substances reduces processing to particle surface, to improve the chemical property of material.As an example, can prepare according to document (Ma Shuhua etc., " electrochemistry ", 1996,2) disclosed method.
Oxidation modification method of the present invention is with oxidizing substance particle surface to be carried out oxide treatment, to improve the chemical property of material.As an example, can prepare according to document (N Tsuyoshi, V Gupta, O Yoshimi etc., the 27th time carbon materials association nd Annual Meeting collection) disclosed method.
Organism coating method of the present invention is with organism process carbonizing treatment, makes it form one deck carbon coated on the material granule surface.As an example, can be according to document (Zhang Xiaolin etc., " the pitch-coated natural graphite is done the research of lithium ion battery negative material ", " charcoal is plain ", 2006 the 4th phases) disclosed method preparation.
Physically modified method of the present invention comprises through mechanical force, Intermolecular Forces (like Van der Waals force, hydrogen bond etc.) inorganic surfaces properties-correcting agent or organic surface modifying agent is adsorbed onto the powder particle surface; Form coating layer on the powder particle surface; To reduce the surface tension of powder; Change the surface polarity of powder particle, the reunion between the minimizing powder particle etc., thereby the pattern and the shape of change particle surface.As an example, can prepare according to document (Huang Yingfen, " inorganic powder surface method of modifying summary ", " Liming Vocation Univ.'s journal ", in March, 2011, the 1st phase) disclosed method.
Doping vario-property method of the present invention is meant through other materials (like metallic element) that mix to improve the chemical property of material.As an example, can be according to document (Cai Yong etc., " electrolysis MnO
2Mechanical ball milling-doping vario-property and the application in ultracapacitor thereof ", " science and technology in enterprise and development ", 2010 the 8th phases) the disclosed method preparation.
The vitriol oil of the present invention is meant that mass concentration is not less than 70% sulfuric acid.
Concentrated nitric acid of the present invention is meant that mass concentration is not less than 60% nitric acid.
Concentrated hydrochloric acid of the present invention is meant that mass concentration is not less than 35% hydrochloric acid.
Crystalline structure according to the invention detects the X-ray diffraction analysis method that adopts, and the Cu-Ka source of radiation is used in this XRD test, and Guan Liuwei 40mA, pipe press and be 40KV, 12 °/min of sweep velocity, and sweep limit 10-90 °, step-length is 0.020 °.
Charge-discharge performance test according to the invention adopts LAND CT2001A battery test system that simulated battery is carried out the constant current charge-discharge test, and the voltage tester scope is 0-1.8V.The making of simulated battery comprises the steps: by certain mass than taking by weighing negative material, conductive carbon black, the pvdf (PVDF) that makes, and active material and conductive carbon black ground it is mixed in mortar, joins in N-Methyl pyrrolidone (NMP) solution of PVDF; Stir; Make slurry, wherein, the mass ratio of active material: conductive carbon black: PVDF is 90: 5: 5; It is coated on the Copper Foil, processes pole piece through oven dry, roll extrusion.Make counter electrode with metal lithium sheet, Celgard2400 is a barrier film, 1mol/L LiPF
6/ EC (NSC 11801)+DMC (dimethyl carbonate)+EMC (methyl ethyl carbonate fat) (volume ratio 1: 1: 1) is an electrolytic solution, in the glove box of logical argon gas, is assembled into simulated battery, carries out electrochemical property test after leaving standstill 12h.
First discharge specific capacity of the present invention=be discharged to first loading capacity/active substance quality of 0V with the electric current of 0.2C.
Initial charge specific storage of the present invention=with the electric current initial charge of 0.2C loading capacity/active substance quality to 1.8V.
Efficient first of the present invention=(initial charge capacity/loading capacity) first * 100%.
Cycle performance of the present invention test comprises: with the current charges of 1C to 1.8V, again with the current discharge of 1C to 0V.
Except as otherwise noted, when the present invention relates to the per-cent between liquid and the liquid, described per-cent is volume per-cent; When the present invention relates to the per-cent between liquid and the solid, said per-cent is volume/weight per-cent; When the present invention relates to the per-cent between solid and the liquid, said per-cent is weight/volume percent; All the other are weight/weight percent.
Compared with prior art, the present invention has following advantage:
(1) synthetic graphite that the present invention is bigger with particle diameter and the less natural graphite uniform mixing of particle diameter; Make the less natural graphite of particle diameter be scattered between the particle of the bigger synthetic graphite of particle diameter; Thereby reduce the hole between the graphite granule, increase the contact area between the particle, reduce internal resistance; Significantly improve the loading capacity of graphite material, can reach 350mAh/g above (even up to more than 368mAh/g);
(2) the present invention carries out surface-treated to improve its cycle performance to graphite material; Enlarge markedly its reversible embedding lithium capacity and first the enclosed pasture efficient; And the graphite material after the surface-treated has good cycle performance; Half-cell is at the 1C rate charge-discharge, and 100 circulation back capability retentions are still at (even up to more than 96.3%) more than 90%, and efficient is up to more than 95.5% first;
(3) the present invention adopts synthetic graphite and the natural graphite that mixes certain weight ratio; When effectively overcoming defectives such as the synthetic graphite electrical capacity is low, the natural graphite cycle performance is relatively poor; Also effectively reduce the manufacturing cost of graphite cathode material, the cost rate of descent is about 1-10%;
(4) preparation technology of the graphite cathode material of heavy body of the present invention is simple, and is easy to operate, is fit to large-scale industrialization production.
Description of drawings
The SEM figure (1000 times of enlargement ratios) of the carbon coating graphite material of Fig. 1 embodiment 3 preparations.
The charging and discharging curve figure of carbon coating graphite material under the 1C multiplying power of Fig. 2 embodiment 3 preparations.
Embodiment
Below will combine embodiment to specify the present invention, embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting essence of the present invention.
Embodiment 1The preparation of graphite composite material of the present invention and detection
The preparation method of graphite composite material of the present invention comprises the steps:
1) with D
50Be the ethanol that the synthetic graphite 200g of 10 μ m places 500ml, mechanical stirring, stir speed (S.S.) 150r/min is uniformly dispersed it, makes synthetic graphite suspension-s;
2) under the agitation condition, with D
50Be that the natural graphite 20g of 5 μ m joins in the synthetic graphite suspension-s that step 1) makes, 350r/min stirred 1 hour, filtered, and dry 8h in 50 ℃ of vacuum drying ovens makes the mixture (claiming graphite mixture again) of synthetic graphite and natural graphite;
4) under the agitation condition, the graphite mixture that step 3) is made joins in the mixing solutions of dioxysulfate water, continues to stir 2 hours; Filter; Being washed with distilled water to pH is 6.5-7.5, and dry 8h in 50 ℃ of vacuum drying ovens makes the graphite mixture of surface-treated; Wherein, described dioxysulfate water mixed solution is that 98% the vitriol oil and mass concentration are that 25% ydrogen peroxide 50 is that configuration in 1: 3 forms according to volume ratio by mass concentration.
By detection method of the present invention, the graphite mixture of the surface-treated that makes is assembled into battery, carry out electrochemical property test, the result sees table 1.
Embodiment 2The preparation of graphite composite material of the present invention and detection
The preparation method of graphite composite material of the present invention comprises the steps:
1) with D
50Be synthetic graphite 200g and the D of 20 μ m
50The natural graphite 40g that is 5 μ m joins in the three-dimensional motion mixer simultaneously, mixes 20min, makes graphite mixture;
2) it is 60% NaBH that the graphite mixture that step 1) is made joins the 2L mass concentration
4In the aqueous solution, be heated to 60 ℃, mechanical stirring 2h filters, and is washed with distilled water to no sodium ion and detects, and dry 8h in 50 ℃ of vacuum drying ovens makes the graphite mixture of surface-treated.
By detection method of the present invention, with step 2) graphite mixture of the surface-treated that makes is assembled into battery, carries out electrochemical property test, and the result sees table 1.
Embodiment 3The preparation of graphite composite material of the present invention and detection
The preparation method of graphite composite material of the present invention comprises the steps:
1) with D
50Be synthetic graphite 180g and the D of 20 μ m
50The natural graphite 30g that is 10 μ m joins in the three-dimensional motion mixer simultaneously, mixes 30min, makes graphite mixture;
2) 27g epoxy resin is dissolved in the 500ml ETHYLE ACETATE, makes the ethyl acetate solution of epoxy resin;
3) graphite mixture that step 1) is made joins step 2) in the ethyl acetate solution of the epoxy resin that makes, wherein, the mass ratio of epoxy resin and graphite mixture is 1: 8; Stir 1h, mix dry 8h in 150 ℃ of vacuum drying ovens; Remove and desolvate, make the graphite mixture precursor;
4) under argon shield, the graphite mixture precursor that step 3) is made carries out high-temperature calcination, wherein, is warming up to 1000 ℃ with the temperature rise rate of 2 ℃/min, and constant temperature 3h reduces to room temperature, obtains the admixed graphite of coated modified carbon.
By detection method of the present invention, the admixed graphite material of the coated modified carbon that obtains is assembled into battery, carry out electrochemical property test, the result sees table 1.
Embodiment 4The preparation of graphite composite material of the present invention and detection
The preparation method of graphite composite material of the present invention comprises the steps:
1) with D
50Be synthetic graphite 200g and the D of 25 μ m
50The natural graphite 25g that is 8 μ m joins in the three-dimensional motion mixer simultaneously, mixes 25min, makes graphite mixture;
2) take by weighing the 40g hard pitch, pulverize, sieve is got the part that particle diameter is not more than 2 μ m, makes the hard pitch crushed material;
3) graphite mixture and the step 2 that step 1) are made) the hard pitch crushed material that makes mixes, and makes the graphite mixture precursor, and wherein, the mass ratio of hard pitch and graphite mixture is 1: 10;
4) under argon shield, the graphite mixture precursor that step 3) is made carries out high-temperature calcination, wherein, is warming up to 950 ℃ with the temperature rise rate of 2 ℃/min, and constant temperature 3h reduces to room temperature, obtains the admixed graphite of coated modified carbon.
By detection method of the present invention, the admixed graphite material of the coated modified carbon that makes is assembled into battery, carry out electrochemical property test, the result sees table 1.
Embodiment 5The preparation of graphite composite material of the present invention and detection
The preparation method of graphite composite material of the present invention comprises the steps:
1) with D
50Be synthetic graphite 200g and the D of 25 μ m
50The natural graphite 50g that is 10 μ m adds in the planetary ball mill, makes dispersion agent with ethanol, 300r/min ball milling 5h, and filtration under diminished pressure is dried in 80 ℃ of vacuum drying ovens, makes graphite mixture;
2) take by weighing the 50g hard pitch, pulverize, sieve is got the part that particle diameter is not more than 2 μ m, makes the hard pitch crushed material;
3) graphite mixture and the step 2 that step 1) are made) the hard pitch crushed material that makes mixes, and the mass ratio of hard pitch and graphite mixture is 1: 8, makes the graphite mixture precursor;
4) under argon shield, the graphite mixture precursor that step 3) is made carries out high-temperature calcination, wherein, is warming up to 800 ℃ with the temperature rise rate of 2 ℃/min, and constant temperature 3h reduces to room temperature, obtains the admixed graphite of coated modified carbon.
By detection method of the present invention, the admixed graphite material of the coated modified carbon that makes is assembled into battery, carry out electrochemical property test, the result sees table 1.
Embodiment 6The preparation of graphite composite material of the present invention and detection
The preparation method of graphite composite material of the present invention comprises the steps:
1) be that the synthetic graphite 210g of 25 μ m and natural graphite 30g that D50 is 10 μ m add in the planetary ball mill with D50, make dispersion agent with ethanol, 280r/min ball milling 5h, filtration under diminished pressure is dried in 80 ℃ of vacuum drying ovens, makes graphite mixture;
2) the 30g furfuryl resin is dissolved in the 150ml ETHYLE ACETATE, makes the ethyl acetate solution of furfuryl resin;
3) graphite mixture that step 1) is made joins step 2) in the ethyl acetate solution of the furfuryl resin that makes, wherein, furfuryl resin and graphite blended mass ratio are 1: 8; Stir 1h, mix dry 8h in 150 ℃ of vacuum drying ovens; Remove and desolvate, make the graphite mixture precursor;
4) under argon shield, the graphite mixture precursor that step 3) is made carries out high-temperature calcination, wherein, is warming up to 1100 ℃ with the temperature rise rate of 2 ℃/min, and constant temperature 3h reduces to room temperature, obtains the admixed graphite of coated modified carbon.
By detection method of the present invention, the admixed graphite material that obtains coated modified carbon is assembled into battery, carry out electrochemical property test, the result sees table 1.
Comparative Examples 1
1) take by weighing the 50g hard pitch, pulverize, sieve is got the part that particle diameter is not more than 2 μ m, makes the hard pitch crushed material;
2) with D
50The synthetic graphite 200g and the hard pitch crushed material that are 15 μ m mix, and make the graphite precursor, and wherein, the mass ratio of hard pitch and synthetic graphite is 1: 8;
3) under argon shield, with step 2) the graphite precursor that makes carries out high-temperature calcination, wherein, is warming up to 1100 ℃ with the temperature rise rate of 2 ℃/min, and constant temperature 3h reduces to room temperature, obtains the synthetic graphite of coated modified carbon.
By described detection method of the present invention, the synthetic graphite material that obtains coated modified carbon is assembled into battery, carry out electrochemical property test, the result sees table 1.
Comparative Examples 2
With D
50Be synthetic graphite 200g and the D of 20 μ m
50The natural graphite 50g that is 5 μ m joins in the three-dimensional motion mixer simultaneously, mixes 30min, obtains admixed graphite.
By detection method of the present invention, the admixed graphite material that obtains is assembled into battery, carry out electrochemical property test, the result sees table 1.
Comparative Examples 3
By detection method of the present invention, with D
50The synthetic graphite material that is 15 μ m is assembled into battery, carries out electrochemical property test, and the result sees table 1.
Comparative Examples 4
By detection method of the present invention, with D
50The natural graphite material that is 5 μ m is assembled into battery, carries out electrochemical property test, and the result sees table 1.
Comparative Examples 5
1) 30g epoxy resin is dissolved in the 150ml ETHYLE ACETATE, makes the ethyl acetate solution of epoxy resin;
2) with D
50Be that the natural graphite 240g of 10 μ m joins in the ethyl acetate solution of the epoxy resin that step 1) makes, stir 1h, mix, dry 8h in 150 ℃ of vacuum drying ovens removes and desolvates, and makes the graphite precursor;
3) under argon shield, with step 2) the graphite precursor that makes carries out high-temperature calcination, wherein, is warming up to 1150 ℃ with the temperature rise rate of 2 ℃/min, and constant temperature 3h reduces to room temperature, obtains the natural graphite of coated modified carbon.
By detection method of the present invention, the coating modification natural graphite material that Comparative Examples 5 is made is assembled into battery, carries out electrochemical property test, and the result sees table 1.
The Electrochemical Properties of table 1 graphite composite material of the present invention
Visible by table 1; With synthetic graphite and natural graphite according to certain mass than after mixing; Again the graphite mixture that makes is carried out surface-treated, significantly improves the chemical property of composite cathode material of silicon/carbon/graphite, its first loading capacity up to 368mAh/g; Efficient is up to more than 95.5% first, and the capability retention after 100 circulations is up to more than 96.3%.
Claims (10)
1. the graphite material of a heavy body; Said graphite material is made up of synthetic graphite and natural graphite; Wherein, The mass ratio of synthetic graphite and natural graphite is 20: 1-1: 1, and the mass ratio of preferred synthetic graphite and natural graphite is 15: 1-3: 1, more preferably the mass ratio of synthetic graphite and natural graphite is 10: 1-4: 1.
2. graphite material according to claim 1; Said graphite material is made up of synthetic graphite and natural graphite; Wherein, The particle shape of said synthetic graphite and natural graphite is selected from sphere, subsphaeroidal, oval, needle-like, tabular, fibrous, lepidiod any or its combination, is preferably sphere, subglobose any or its combination.
3. according to each described graphite material of claim 1-2, the meta particle diameter (D of said synthetic graphite
50) be 1-80 μ m, be preferably 10-70 μ m, more preferably 2050 μ m.
4. according to each described graphite material of claim 1-3, the D of said natural graphite
50Be 1-80 μ m, be preferably 5-60 μ m, more preferably 10-40 μ m.
5. according to each described graphite material of claim 1-4; The mixture of described synthetic graphite, natural graphite or synthetic graphite and natural graphite carries out surface-treated; The method of preferred said surface-treated is selected from any or its combination that reduction modification method, oxidation modification method, organism coat method, physically modified method, doping vario-property method; The method of surface reduction modification more preferably, oxidation modification method, organism coat any or its combination of method; Wherein, preferred said reduction modification is selected from LiAlH with reductive agent
4, NaBH
4, LiBH
4, Al (BH
4)
3, oxalic acid, Hypophosporous Acid, 50, sodium hypophosphite, Sulfothiorine, tin protochloride any or its combination; More preferably said oxidation modification is selected from the vitriol oil, concentrated nitric acid, O with oxygenant
2, ydrogen peroxide 50, ozone, hypochlorous acid, concentrated hydrochloric acid, potassium perchlorate, potassium permanganate, iodine, bromine water any or its combination.
6. according to each described graphite material of claim 1-5; Said organism coating method is selected from vapour deposition and coats method, liquid phase and coat method, fusion and coat any or its combination that method, solid phase mixing coat method; Be preferably solid phase mixing and coat any or its combination that method, liquid phase coat method; The organism that uses in the preferred said organism coating method is selected from any or its combination of mid-temperature pitch, hard pitch, secondary coal-tar pitch, petroleum pitch, coal tar, Z 150PH, styrene-butadiene rubber(SBR), CMC 99.5, PS, SE, polyacrylonitrile, resol, furfuryl resin, epoxy resin, glucose, sucrose, fructose, Hydrocerol A, Mierocrystalline cellulose, starch, is preferably any or its combination of mid-temperature pitch, resol, furfuryl resin, epoxy resin, sucrose, Hydrocerol A.
7. the preparation method of the graphite material of each described heavy body of claim 1-6 is characterized in that, said graphite material is made up of synthetic graphite and natural graphite, and the mass ratio of synthetic graphite and natural graphite is 20: 1-1: 1, comprise the steps:
(1) takes by weighing the synthetic graphite and the natural graphite of aequum, with its uniform mixing;
(2) synthetic graphite behind the uniform mixing and natural graphite mixture are carried out surface-treated,
Wherein, the mass ratio of preferred synthetic graphite and natural graphite is 15: 1-3: 1, and more preferably the mass ratio of synthetic graphite and natural graphite is 10: 1-4: 1.
8. preparation method according to claim 7, the described blending means of step (1) are selected from any or its combination of ball mill mixing method, dispersion agent dispersing and mixing method, mixing machine hybrid system.
9. according to claim 7 or 8 described preparing methods; Said synthetic graphite is selected from any or its combination that oil is needle coke, coal-based needle coke, MCMB, hard charcoal; Be preferably MCMB, more preferably described natural graphite is selected from natural flake graphite.
10. each described graphite material of claim 1-6 or each preparation method of claim 7-9 prepare the application that the graphite material of gained is used for preparing lithium ion battery.
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