CN1702893A - Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof - Google Patents
Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof Download PDFInfo
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- CN1702893A CN1702893A CNA2005100343303A CN200510034330A CN1702893A CN 1702893 A CN1702893 A CN 1702893A CN A2005100343303 A CNA2005100343303 A CN A2005100343303A CN 200510034330 A CN200510034330 A CN 200510034330A CN 1702893 A CN1702893 A CN 1702893A
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- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000010406 cathode material Substances 0.000 title description 5
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 42
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- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
This invention discloses one lithium battery negative electrode materials and its process method, wherein, the battery negative electrode, battery, lithium battery negative material comprise sphere natural graphite and the irregular shape carbon with low crystal degree; the natural graphite core has the radius proportion of one to three micro characteristics. The process method comprises the following steps: grinding the natural graphite and shaping and purification processing; surface decoration and mixture with the carbon materials; mixture materials processing.
Description
Technical field
The present invention relates to a kind of cathode material for high capacity lithium ion battery and preparation method thereof, and the lithium ion battery negative and the lithium ion battery that adopt this cathode material for high capacity lithium ion battery.
Background technology
Negative material is the key that lithium ion battery is realized miniaturization, high capacity.The negative material that extensively adopts in the lithium ion battery production at present is a carbon element class material, during charging, and Li
+The interlayer that embeds graphite-structure forms similar LiC
6Molecular structure.Graphite-like carbon negative pole material springy texture, the function admirable of reversible doff lithium has charge and discharge platform preferably, and security performance is good, but such material capacity is limited, and theoretical capacity is 372mAh/g.Because the degree of graphitization of native graphite is higher, the edge of carbon crystallite and the crystal structure between the bottom surface and other physicochemical properties difference are bigger, stronger with the inhomogeneities of electrolyte reaction, and the decomposition reaction of electrolyte mainly occurs in the marginal portion of carbon crystallite, so the compactness of the passivating film that generates is relatively poor, in charging process, the common embedding of solvation lithium ion takes place easily, cause the expansion and the collapse of graphite linings, increased irreversible capacity.After native graphite process physics or chemical method were handled in addition, it was poor to exist with the adhesive property of pole plate, is easy to come off from pole plate in the cycle charge discharge electric process, has influenced cycle life, the cycle life when especially having reduced high current charge-discharge.In order to improve the chemical property of graphite material, people carry out modification and finishing by the whole bag of tricks to native graphite.As E.Electrchem.Commun.2000,2, Wu in 272, Y.P. wait and graphite is carried out oxidation improve its performance, J.of the Electrochem.Soc.2000, Yoshio in 147,1245, M. wait and adopt the method that coats to graphite modified, Hidetoshi Honbo etc. handle graphite with the method for machinery, chemical modification.In these processing methods, ubiquity complex disposal process, and technical process is wayward, and cost is higher, can't take into account the defectives such as raising of the combination property of battery, has influenced batch process and industrialization.In addition, because native graphite is shorter as the application time of lithium ion battery negative material, and native graphite itself has unique crystal and surface texture, if prepare negative pole and assembled battery often can not reach good effect according to common process, thereby causes the overall performance of battery to descend.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion battery cathode material and its preparation method, battery cathode, battery, the technical problem that solves is to improve the reversible specific capacity and the cyclical stability of cell negative electrode material, simplify the treatment process of negative material, reduce cost, improve the overall performance of lithium ion battery.
The present invention is by the following technical solutions: a kind of lithium ion battery negative material, described negative material comprises spherical natural graphite and coats its low-crystallinity amorphous carbon that the native graphite core has sphere or the microscopic feature of almost spherical, the crystal structure of graphite crystal carbon atom aspect closed end and the open pores density of 500～1500/μ m of draw ratio 1～3.
A kind of preparation method of lithium ion battery negative material, its step comprises: one, the native graphite with degree of crystallinity 83～96% also passes through low speed nodularization pulverizer and grader shaping and spheroidization through the high speed disintegrator mechanical crushing; Two, the native graphite behind the spheroidization is carried out purification process, the fixed carbon content that makes graphite after the purification process is greater than 99.9%; Three, the graphite powder after the purification process is carried out finishing, form the open pores density of crystal structure and 500～1500/μ m with graphite crystal carbon atom aspect closed end; Four, the graphite after the finishing is mixed with 1～30% material with carbon element predecessor form compound; Five, compound is put into heat-treatment furnace, in a vacuum or be heated to 600～1200 ℃ in the protective atmosphere of non-oxidizing gas, be incubated 0.5～24 hour, reduce to room temperature then, form low-crystallinity amorphous carbon at graphite surface.
High speed disintegrator of the present invention is high-speed rotary pulverizer, airslide disintegrating mill, high pressure flour mill or bar type mechanical crusher; Low speed nodularization pulverizer is low velocity impact formula nodularization pulverizer, air-flow vortex formula pulverizer, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer; Grader is gas flow sizing machine, jet classifying machine, sub-micron grader or ultra micro rice gas flow sizing machine.
Finishing of the present invention is adopted and, is heated in inert gas and handled more than 800 ℃ 4～5 hours after 2～3 hours through 500～800 ℃ of oxidation processes, fluorination treatment or hydrogenation treatment.
Material with carbon element predecessor of the present invention is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt, and predecessor proportion in graphite material is 1～30%.
Non-oxidizing gas of the present invention is nitrogen, argon gas, helium, neon or carbon dioxide.
Non-oxidizing gas flow of the present invention is 1～5L/min.
The present invention puts into heat-treatment furnace with compound, and in a vacuum or be heated in the protective atmosphere of non-oxidizing gas in 600～1200 ℃ the process, programming rate is 1～20 ℃/minute.
A kind of lithium ion battery negative, comprise cell negative electrode material, conductive agent and binding agent, described cell negative electrode material adopts spherical natural graphite to be coated with the low-crystallinity amorphous carbon material, and the weight ratio of cell negative electrode material, conductive agent and binding agent is: 99.1～82: 0.6～11: 0.3～7.
Conductive agent of the present invention is selected the mixture of graphite, carbon black or graphite and carbon black for use, and graphite is 0～1: 1～2 with the mixture weight ratio of carbon black; Binding agent is selected the mixture of the N-methyl pyrrolidone solution of Kynoar, water miscible LA-133, butadiene-styrene rubber breast, sodium carboxymethylcellulose or butadiene-styrene rubber breast and sodium carboxymethylcellulose for use, and the butadiene-styrene rubber breast is 1～4: 0～3 with the mixture weight ratio of sodium carboxymethylcellulose.
A kind of lithium ion battery negative, comprise cell negative electrode material, conductive agent and binding agent, described cell negative electrode material adopts spherical natural graphite to be coated with low-crystallinity amorphous carbon, conductive agent is a carbon black, binding agent is butadiene-styrene rubber breast and sodium carboxymethylcellulose, and the weight ratio of cell negative electrode material, carbon black, butadiene-styrene rubber breast and sodium carboxymethylcellulose is 95: 1: 2.5: 1.5.
A kind of lithium ion battery, comprise negative pole, anodal, electrolyte and barrier film, described negative material is that spherical natural graphite is coated with low-crystallinity amorphous carbon, anodal transition metal oxide by the embedding lithium constitutes, and electrolyte is organic mixed solvent solution of the lithium salts of concentration 1M, and barrier film is the high molecular polymer microporous membrane.
Transition metal oxide of the present invention is selected cobalt acid lithium, lithium nickelate, LiMn2O4 or LiFePO4 for use; Lithium salts is selected lithium perchlorate, lithium hexafluoro phosphate or hexafluoroarsenate lithium for use; Organic solvent is selected ethylene carbonate, dimethyl carbonate or methyl ethyl carbonate for use, any two combinations of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate or three kinds of combinations, the volume ratio of two kinds of combinations is 1～9: 9～1, and the volume ratio of three kinds of combinations is 1: 1: 1; Barrier film is polyethylene, polypropylene or poly-second/propylene composite micro porous film.
The present invention compared with prior art, the native graphite lattice carbon atom aspect end of cell negative electrode material has big open pores density structure, increased the charge/discharge capacity of negative material, and because the end construction of graphite lattice carbon atomic layer closure makes electrolyte be difficult for infiltrating graphite layers, prolonged cycle life, and after adopting low-crystallinity amorphous carbon to coat, the specific area of negative material is descended, improved the coulombic efficiency that discharges and recharges of battery, further improve the comprehensive electro-chemical properties of negative material, improved the overall performance of lithium ion battery negative and battery.
Description of drawings
Fig. 1 is the grain shape photo that lithium ion battery negative material of the present invention is taken under high resolution electron microscope (HREM).
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.As shown in Figure 1, lithium ion battery negative material of the present invention, it is a kind of composite material with nuclear, shell structure, wherein the core of composite graphite is a kind of native graphite particulate, external coating is one deck amorphous carbon with low-crystallinity, the native graphite core has the microscopic feature of draw ratio 1～3 sphere or almost spherical, the open pores density of the crystal structure of graphite crystal carbon atomic layer closed end and 500～1500/μ m.
Inventor of the present invention finds by the microstructure and the relation between its chemical property of system research native graphite, the graphite granule surface is after handling through specific finishing, can be combined into closed end construction in the end of lamellar graphite crystal and adjacent lattice aspect pairing, between two adjacent layering closing structures, can keep certain open-ended hole, and the density of open pores, the discharge capacity of the quantity appreciable impact negative material of unit length open pores.According to molecular orbital theory, lithium ion is implemented in the embedding in the graphite material and deviates from charge and discharge process, and the position that most probable passes through is exactly the open pores position between the graphite linings closed ends.Because at these open pores places, a little less than the interaction between carbon atom and lithium ion, reduced the energy barrier that lithium ion enters, thereby allowed a large amount of lithium ions therefrom to pass.Therefore, along with the increase of the open-ended void density of carbon atom plane layer of graphite linings lattice, lithium ion is easier to be entered and deviates from, and then has increased charge/discharge capacity.On the other hand, if the carbon atom flat end of graphite be opening and do not form the structure of part closure, be easy to take place the common embedding of solvent and lithium ion like this, cause graphite stripping layer, capacity and cycle performance descend; And, cause electrolyte decomposition because the chemism of open end is excessive, the chemical property of negative pole is descended.Studies show that it is the most reasonable in the scope of 100～1500/μ m that graphite has open-ended void density.
Make graphite produce the carbon atom plane layer of above-mentioned closed end and the open pores density of some arranged, can adopt various powder handlings and surface modification method to realize, as mechanical crushing, surface oxidation, fluoridize, hydrogenation and later stage heat treatment.If the open pores density that makes closed ends carbon atom plane layer is at about 100/μ m, then generally only needing high speed disintegrator to handle gets final product, but reach higher open pores density, must add other finishing handles, such as adopting 500 ℃～800 ℃ oxidation processes, adopt later on the later stage heat treatment in the inert atmosphere under 800 ℃ or the higher temperature again, can realize the open pores density of 500～1500/μ m.
The present invention adopts said method to handle material of main part---native graphite micro mist, make it to have the closed ends structure on the graphite linings lattice carbon atom plane of bigger open pores density, increased the charge/discharge capacity of negative material, and because the end construction of graphite lattice c plane closure makes electrolyte be difficult for infiltrating graphite layers, prolonged cycle life, and after adopting low-crystallinity amorphous carbon to coat, the specific area of negative material is descended, improve the coulombic efficiency that discharges and recharges of battery, further improved the comprehensive electro-chemical properties of negative material.
The preparation method of lithium ion battery negative material of the present invention, may further comprise the steps: one, be that 83～96% native graphite is pulverized through high-speed rotary pulverizer, airslide disintegrating mill, high pressure flour mill or bar type mechanical crusher degree of crystallinity, secondly through low velocity impact formula nodularization pulverizer, air-flow vortex formula pulverizer, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer spheroidization, again through gas flow sizing machine, jet classifying machine, sub-micron grader or the shaping of ultra micro rice gas flow sizing machine; Two, adopt chemical purification and high temperature purification to carry out purification process the native graphite behind the spheroidization, remove the impurity in the graphite material, make its fixed carbon content greater than 99.9%; Three, with above-mentioned graphite powder through 500～800 ℃ of oxidation processes, fluorination treatment or hydrogenation treatment after 2～3 hours, heating is handled more than 800 ℃ and was carried out finishing in 4～5 hours in inert gas, forms the open pores density of crystal structure and 500～1500/μ m with graphite crystal carbon atomic layer closed end; Four, with above-mentioned high purity graphite and material with carbon element predecessor furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt, mixed on mixer 1～5 hour, predecessor proportion in graphite material is 1～99%; Five, above-mentioned compound is put into heat-treatment furnace; in vacuum or gas is nitrogen, argon gas, helium, neon or carbon dioxide; flow velocity is heat treatment during 1～5 liter/minute gas stream is protected; programming rate is 1～20 ℃/minute; 600～1200 ℃ of insulations 0.5～24 hour; reduce to room temperature then, form low-crystallinity amorphous carbon at graphite surface.
Battery cathode of the present invention comprises cell negative electrode material, conductive agent and binding agent, and cell negative electrode material adopts has spherical natural graphite, and spherical natural graphite is coated with low-crystallinity amorphous carbon; The weight ratio of cell negative electrode material, conductive agent and binding agent is: 99.1～82: 0.6～11: 0.3～7; Conductive agent is selected the mixture of graphite, carbon black or graphite and carbon black for use, and graphite is 0～1: 1～2 with the mixture weight ratio of carbon black; Binding agent is selected the mixture of the methyl pyrrolidone solution of Kynoar, water miscible LA-133, butadiene-styrene rubber breast SBR, sodium carboxymethylcellulose or butadiene-styrene rubber breast SBR and sodium carboxymethylcellulose CMC for use, and butadiene-styrene rubber breast SBR is 1～4: 0～3 with the mixture weight ratio of sodium carboxymethylcellulose CMC; Conductive agent also can be carbon black, and binding agent is butadiene-styrene rubber breast SBR and sodium carboxymethylcellulose CMC, and the weight ratio of cell negative electrode material, carbon black, butadiene-styrene rubber breast SBR and sodium carboxymethylcellulose CMC is 95: 1: 2.5: 1.5.
Battery of the present invention, comprise negative pole, anodal, electrolyte and barrier film, the nucleocapsid structure composite material that negative material is made up of spherical natural graphite and amorphous carbon, spherical natural graphite is coated with low-crystallinity amorphous carbon, and anodal transition metal oxide by the embedding lithium constitutes, electrolyte is organic mixed solvent solution of the lithium salts of concentration 1M, and barrier film is the high molecular polymer microporous membrane; Transition metal oxide is selected cobalt acid lithium, lithium nickelate, LiMn2O4 or LiFePO4 for use; Lithium salts is selected lithium perchlorate, lithium hexafluoro phosphate or hexafluoroarsenate lithium for use; Organic solvent is selected ethylene carbonate, dimethyl carbonate or methyl ethyl carbonate for use, any two combinations of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate or three kinds of combinations, the volume ratio of two kinds of combinations is 1～9: 9～1, and the volume ratio of three kinds of combinations is 1: 1: 1; Barrier film is polyethylene, polypropylene or poly-second/propylene composite micro porous film.
Embodiment 1:
The native graphite of degree of crystallinity 83% is pulverized through the velocity of rotation of high-speed rotary pulverizer 6000rpm, pass through low velocity impact formula nodularization pulverizer spheroidization under the velocity of rotation of 3000rpm again, gas flow sizing machine carries out the chemical purification purification process after adjusting granularity, make its fixed carbon content greater than 99.9%, afterwards through 600 ℃ of oxidation processes 3 hours, argon atmospher middle and later periods heat treatment 5 hours, the open pores density that obtains having closed ends carbon atom plane layer was 780/μ m.The fire stons oil asphalt mixed 2 hours in taking by weighing above-mentioned graphite 180 grams and 20 restraining, and under 5 liters/minute nitrogen current, was warming up to 1000 ℃ with 10 ℃/minute speed, was incubated 2 hours, reduced to room temperature then and obtained composite graphite.
The gained composite graphite prepares electrode as follows: take by weighing 95 gram composite graphites, add 1 gram carbon black, butadiene-styrene rubber breast SBR 2.5 grams, sodium carboxymethylcellulose CMC 1.5 grams, adds an amount of pure water dispersant even after, make electrode.
With lithium is to electrode, 1MLiPF
6Three component mixed solvent EC: DMC: EMC=1: 1: 1, v/v solution was electrolyte, and poly-second/the propylene composite micro porous film is a barrier film, is assembled into simulated battery, with 0.5mA/cm
2Current density carry out constant current charge-discharge experiment, charging/discharging voltage is 0～2.0 volt, test compound graphite reversible specific capacity is 367mAh/g.Cycle performance adopts the finished product battery testing, with LiCoO
2Be positive pole, 1MLiPF
6Three component mixed solvent EC: DMC: EMC=1: 1: 1, v/v solution was electrolyte, and poly-second/the propylene composite micro porous film is a barrier film, be assembled into the finished product battery, speed with 1C discharges and recharges test, and charging/discharging voltage is limited in 4.2～3.0 volts, and recording 500 capability retentions of circulation is 85%.
Embodiment 2:
The native graphite of degree of crystallinity 96% is pulverized through the velocity of rotation of airslide disintegrating mill 6000rpm, pass through air-flow vortex formula pulverizer spheroidization under the velocity of rotation of 3000rpm again, the jet classifying machine carries out the high temperature purification purification process after adjusting granularity, make its fixed carbon content greater than 99.9%, afterwards through 500 ℃ of fluorination treatment 2.5 hours, argon atmospher middle and later periods heat treatment 4.5 hours, the open pores density that obtains having closed ends carbon atom plane layer was 500/μ m.Take by weighing pretreated graphite 170 grams, mixed 3 hours, under 4 liters/minute argon gas stream, be warming up to 900 ℃, be incubated 3 hours, reduce to room temperature then with 20 ℃/minute speed with 30 gram coke.The gained composite graphite prepares electrode and assembled battery by the method for embodiment 1, and recording reversible capacity is 361mAh/g, and 500 times capability retention is 81%.
Embodiment 3:
The native graphite of degree of crystallinity 85% is pulverized through the velocity of rotation of bar type mechanical crusher 6000rpm, pass through micronizer spheroidization under the velocity of rotation of 3000rpm again, the sub-micron grader carries out the high temperature purification purification process after adjusting granularity, make its fixed carbon content greater than 99.9%, afterwards through 800 ℃ of hydrogenation treatment 3 hours, argon atmospher middle and later periods heat treatment 5 hours, the open pores density that obtains having closed ends carbon atom plane layer is 1500/μ m, take by weighing above-mentioned graphite 140 grams and 60 and restrain that polypropylene is fine to be mixed 2 hours, under 1 liter/minute helium flow, be warming up to 1200 ℃ with 1 ℃/minute speed, be incubated 0.5 hour, reduce to room temperature then and obtain composite graphite.
The gained composite graphite prepares electrode as follows: take by weighing composite graphite 94 gram, and with 2 gram carbon blacks, butadiene-styrene rubber breast SBR 3 grams, sodium carboxymethylcellulose CMC 1 gram is made electrode after adding an amount of pure water dispersant.Recording reversible capacity after the method assembled battery by embodiment 1 is 354mAh/g, and 500 times capability retention is 84%.
Embodiment 4:
90% native graphite is pulverized through the velocity of rotation of high pressure flour mill 6000rpm, pass through ultra micro ball mill spheroidization under the velocity of rotation of 3000rpm again, ultra micro rice gas flow sizing machine carries out the chemical purification purification process after adjusting granularity, make its fixed carbon content greater than 99.9%, afterwards through 800 ℃ of oxidation processes 3 hours, argon atmospher middle and later periods heat treatment 5 hours, the open pores density that obtains having closed ends carbon atom plane layer was 1400/μ m.Take by weighing above-mentioned graphite 150 grams and mixed 2 hours, under 5 liters/minute nitrogen current, be warming up to 1200 ℃, be incubated 24 hours, reduce to room temperature then and obtain composite graphite with 10 ℃/minute speed with 50 gram polytetrafluoroethylene.Method by embodiment 1 prepares electrode.
Adopt 1MLiCl0 during assembled battery
41: 1 mixed solvent solution of EC+DMC volume ratio be electrolyte.Recording reversible capacity after the method assembled battery by embodiment 1 is 352mAh/g, and 500 times capability retention is 82%.
Embodiment 5:
Method by embodiment 1 prepares composite graphite material and electrode, and it is anodal adopting LiMn2O4 during assembling finished product battery.Recording reversible capacity after the method assembled battery by embodiment 1 is 367mAh/g, and 500 times capability retention is 83%.
Embodiment 6:
Native graphite is pulverized through the velocity of rotation of high-speed rotary pulverizer 5000rpm, pass through low velocity impact formula nodularization pulverizer spheroidization under the velocity of rotation of 2500rpm again, carry out purification process after adjusting granularity, afterwards through 650 ℃ of oxidation processes 2 hours, afterwards argon atmospher middle and later periods heat treatment 4 hours, the open pores density that obtains having closed ends carbon atom plane layer is 600/μ m.According to the method coated graphite identical with embodiment 1, preparation negative pole and assembled battery and carry out the electro-chemical properties test, recording reversible capacity is 359mAh/g afterwards, and 500 times capability retention is 87%.
Embodiment 7:
Handle graphite, preparation negative pole and battery according to the method identical with example 5, only different is that clad material is selected furane resins for use, and covering amount is 10%.Recording reversible capacity is 368mAh/g, and 500 times the circulation volume conservation rate is 87%.
Embodiment 8:
Handle graphite, preparation negative pole and battery according to the method identical with example 5, only different is that clad material is selected phenolic resins for use, and covering amount is 12%.Recording reversible capacity is 365mAh/g, and 500 times the circulation volume conservation rate is 85%.
Comparative example:
Handle according to the method identical with embodiment 1, only different is that native graphite directly uses as negative material without coating to handle.Recording reversible capacity is 345mAh/g, and 500 times the circulation volume conservation rate is 62%.
It is primary raw material that the present invention adopts native graphite, through efflorescence, purifying and oxidation, some row surface modification treatment such as later stage heat treatment, make the interlayer of graphite produce closed end and have the microstructure of certain opening void density, play the effect of lithium ion turnover graphite layers passage, increased charge/discharge capacity, coat through the surface after the modification and modification of low-crystallinity amorphous carbon layer, the technology of preparation negative pole of the present invention and assembled battery and match materials method, the combination property of battery is significantly improved, when having high discharge capacity, cycle performance is good, greatly promote the ratio of performance to price of native graphite, will become the preferred material of lithium ion battery.
Advantage of the present invention is: negative material adopts the compound amorphous carbon material of native graphite, and material source is extensive, the preparation method is simple, cost is low; The lithium ion battery negative that prepared composite graphite and conductive agent, binding agent constitute has good lithium storage performance; The prepared composite graphite reversible specific capacity of the present invention is greater than 350mAh/g, and 500 capability retentions that circulate are greater than 80%.
Lithium ion battery of the present invention can be widely used in portable electric instrument, instruments such as mobile phone, notebook computer, camcorder apparatus, can be made into the different shape that varies in size, and is applicable to the various electrical domains of using.
Claims (13)
1. lithium ion battery negative material, it is characterized in that: described negative material comprises spherical natural graphite and coats its low-crystallinity amorphous carbon that the native graphite core has sphere or the microscopic feature of almost spherical, the crystal structure of graphite crystal carbon atom aspect closed end and the open pores density of 500～1500/μ m of draw ratio 1～3.
2. the preparation method of a lithium ion battery negative material, its step comprises: one, with the native graphite of degree of crystallinity 83～96% through the high speed disintegrator mechanical crushing and through low speed nodularization pulverizer and grader shaping and spheroidization; Two, the native graphite behind the spheroidization is carried out purification process, the fixed carbon content that makes graphite after the purification process is greater than 99.9%; Three, the graphite powder after the purification process is carried out finishing, form the open pores density of crystal structure and 500～1500/μ m with graphite crystal carbon atom aspect closed end; Four, the graphite after the finishing is mixed with 1～30% material with carbon element predecessor form compound; Five, compound is put into heat-treatment furnace, in a vacuum or be heated to 600～1200 ℃ in the protective atmosphere of non-oxidizing gas, be incubated 0.5～24 hour, reduce to room temperature then, form low-crystallinity amorphous carbon at graphite surface.
3. the preparation method of lithium ion battery negative material according to claim 2, it is characterized in that: described high speed disintegrator is high-speed rotary pulverizer, airslide disintegrating mill, high pressure flour mill or bar type mechanical crusher; Low speed nodularization pulverizer is low velocity impact formula nodularization pulverizer, air-flow vortex formula pulverizer, micronizer, ultra micro ball mill, internal classification impact type micro mist pulverizer or pendulum type ring roll pulverizer; Grader is gas flow sizing machine, jet classifying machine, sub-micron grader or ultra micro rice gas flow sizing machine.
4. the preparation method of lithium ion battery negative material according to claim 3, it is characterized in that: described finishing is adopted and, is heated in inert gas and handled more than 800 ℃ 4～5 hours after 2～3 hours through 500～800 ℃ of oxidation processes, fluorination treatment or hydrogenation treatment.
5. the preparation method of lithium ion battery negative material according to claim 4, it is characterized in that: described material with carbon element predecessor is furane resins, Lauxite, ethyl-amine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, Kynoar, polyacrylonitrile, coke, coal tar pitch or petroleum asphalt, and predecessor proportion in graphite material is 1～30%.
6. the preparation method of lithium ion battery negative material according to claim 5, it is characterized in that: described non-oxidizing gas is nitrogen, argon gas, helium, neon or carbon dioxide.
7. the preparation method of lithium ion battery negative material according to claim 6, it is characterized in that: described non-oxidizing gas flow is 1～5L/min.
8. the preparation method of lithium ion battery negative material according to claim 7; it is characterized in that: described compound is put into heat-treatment furnace; in a vacuum or be heated in the protective atmosphere of non-oxidizing gas in 600～1200 ℃ the process, programming rate is 1～20 ℃/minute.
9. lithium ion battery negative, comprise cell negative electrode material, conductive agent and binding agent, it is characterized in that: described cell negative electrode material adopts spherical natural graphite to be coated with the low-crystallinity amorphous carbon material, and the weight ratio of cell negative electrode material, conductive agent and binding agent is: 99.1～82: 0.6～11: 0.3～7.
10. lithium ion battery negative according to claim 9 is characterized in that: described conductive agent is selected the mixture of graphite, carbon black or graphite and carbon black for use, and graphite is 0～1: 1～2 with the mixture weight ratio of carbon black; Binding agent is selected the mixture of the N-methyl pyrrolidone solution of Kynoar, water miscible LA-133, butadiene-styrene rubber breast, sodium carboxymethylcellulose or butadiene-styrene rubber breast and sodium carboxymethylcellulose for use, and the butadiene-styrene rubber breast is 1～4: 0～3 with the mixture weight ratio of sodium carboxymethylcellulose.
11. lithium ion battery negative, comprise cell negative electrode material, conductive agent and binding agent, it is characterized in that: described cell negative electrode material adopts spherical natural graphite to be coated with low-crystallinity amorphous carbon, conductive agent is a carbon black, binding agent is butadiene-styrene rubber breast and sodium carboxymethylcellulose, and the weight ratio of cell negative electrode material, carbon black, butadiene-styrene rubber breast and sodium carboxymethylcellulose is 95: 1: 2.5: 1.5.
12. lithium ion battery, comprise negative pole, anodal, electrolyte and barrier film, it is characterized in that: described negative material is that spherical natural graphite is coated with low-crystallinity amorphous carbon, anodal transition metal oxide by the embedding lithium constitutes, and electrolyte is organic mixed solvent solution of the lithium salts of concentration 1M, and barrier film is the high molecular polymer microporous membrane.
13. battery according to claim 12 is characterized in that: described transition metal oxide is selected cobalt acid lithium, lithium nickelate, LiMn2O4 or LiFePO4 for use; Lithium salts is selected lithium perchlorate, lithium hexafluoro phosphate or hexafluoroarsenate lithium for use; Organic solvent is selected ethylene carbonate, dimethyl carbonate or methyl ethyl carbonate for use, any two combinations of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate or three kinds of combinations, the volume ratio of two kinds of combinations is 1～9: 9～1, and the volume ratio of three kinds of combinations is 1: 1: 1; Barrier film is polyethylene, polypropylene or poly-second/propylene composite micro porous film.
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