CN102364727A - Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material - Google Patents
Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material Download PDFInfo
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Abstract
The invention provides a hard carbon micro-spherical composite anode material of a lithium battery and a preparation method for the hard carbon micro-spherical composite anode material, which belong to the technical field of anode materials of lithium ion batteries. The material is formed by compounding starch-based hard carbon microspheres and expanded graphite, wherein the expanded graphite is used as a template; the starch-based hard carbon microspheres are embedded into the gap of the expanded graphite; and a graphite sheet layer surrounds the starch-based hard carbon microspheres to form an artificial solid space conductive network. The preparation method comprises the following steps of: preparing the starch-based hard carbon microspheres; mixing; washing; shaking; separating; and drying, and thus obtaining the hard carbon micro-spherical composite anode material. Due to the adoption of a special structure of the expanded graphite, the expanded graphite and the starch-based hard carbon microspheres are compounded to prepare the anode material, and a good channel is provided for electronic conduction due to the construction of a solid space network structure, so that the voltage hysteresis effect of a hard carbon material is improved, and the initial efficiency of the anode material is improved.
Description
Technical field
The present invention relates to a kind of lithium battery material and preparation method thereof, more particularly, the present invention relates to hard carbon microspheres composite negative pole material of a kind of lithium battery and preparation method thereof, belong to the lithium ion battery negative material technical field.
Background technology
At present, the research of lithium ion battery carbon cathode and use mainly round graphitized charcoal and difficult graphitized charcoal (hard charcoal) two big types of materials and launch.What extensive use was gone up in industry now is Delanium, but the capacity of its 372mAh/g is low excessively, more and more can not satisfy the requirement of market development.And because graphite has layer structure, therefore when lithium ion get into layer with layer the gap in, will make graphite volumetric expansion about 10%.If charge rate is too fast, effect is too violent, will cause peeling off of graphite, even the short circuit blast.Why charge rate is slow for general commercially available battery, is exactly for fear of this danger mainly.Therefore, people's diversion to other material, for example soft charcoal, hard charcoal, charcoal/silicon composite, metal oxide etc.With regard to existing market, hard charcoal has been realized the commercial application of certain scale in the novel negative material, and other material also is in the laboratory development mostly because the defective of self does not overcome as yet well.
Hard charcoal has caused people's very big interest with higher capacity, low cost and the excellent cycle performance that its random ordering was had.Sony company obtains the raw material of wood-charcoal material that specific capacity is 450mAh/g through the thermal depolymerization furfuryl alcohol; The reversible capacity that Kanebo company makes the pyrolytic carbon negative material of presoma with polyphenyl phenol reaches 580mAh/g, the theoretical embedding lithium capacity 372mAh/g of graphite-like raw material of wood-charcoal material head and shoulders above, thus make people carry out a large amount of research and development to it.In order to improve the volume energy density of hard raw material of wood-charcoal material, Ou Jung Kwon etc. are that raw material has been processed hard charcoal ball with phenolic resins, and it has higher compacted density (0.9g/mL) and less specific area (with respect to irregular hard charcoal class material).Employing hydrothermal methods such as Wang have prepared a kind of nanostructured microsphere carbon cathode material; It is that the outward appearance diameter is the charcoal ball of 5～10 μ m; In the ball nano-pore or the pipe of the aperture of single graphite linings composition at 0.5～3.0 nm; It has combined the height storage lithium ability of carbon nano-tube material and the excellent processing characteristics of spherical material with carbon element, and energy density is higher by 30% than the MCMB material that is using at present, reaches 400 mAh/g; The needs that are particularly useful for the big current work of lithium-ion-power cell, and cost is well below CNT.The fail safe aspect, coal gasification company in Osaka uses coal tar pitch to be raw material, makes hard raw material of wood-charcoal material through 1100 ℃ of charings, and through analyzing, this hard raw material of wood-charcoal material is crossed to put and lithium metal just can take place in 120% o'clock separated out, and by comparison, graphite cathode is crossed to put promptly had lithium to separate out at 105% o'clock.Therefore, consider that hard raw material of wood-charcoal material is better than graphite from the security performance of battery.But; Because the design feature of hard charcoal itself; The charging and discharging curve of typical hard raw material of wood-charcoal material has bigger first charge-discharge irreversible capacity (generally greater than 20%) and voltage delay phenomenon (discharge potential is apparently higher than the charged electric potential of the embedding lithium state of correspondence), and it has hindered its large-scale commercial applications use on lithium ion battery.
Expanded graphite is claimed flexible graphite again, is to be raw material with the natural flake graphite, generates graphite intercalation compound through chemical treatment earlier, and promptly expansible graphite is processed expanded graphite through high-temperature process again.When expansible graphite was heat-treated, these intercalation compound generation decomposition reactions also discharged a large amount of gas at short notice, and under the effect of gas motive force, graphite flake layer moves along the z direction of principal axis; Because the uneven distribution of intercalation compound; The displacement that causes each graphite flake layer to move has nothing in common with each other; The result makes expanded graphite produce the different hole of size, the position that decomposition reaction or gas motive force fail to arrive does not take place then still keep the original lamella packed structures of graphite, forms hole wall.Graphite has typical anisotropic structure, is about 2.5 * 10 along the conductivity that is parallel to the carbon plane direction
6S/m, perpendicular to the conductivity of carbon plane direction then much smaller than this numerical value.
In the lithium cell cathode material research field, the relevant rare report of problem that the hard carbon microspheres of starch base/the expanded graphite conductivity of composite material can change.
Summary of the invention
The charging and discharging curve that the present invention is intended to solve hard raw material of wood-charcoal material in the prior art has the bigger first charge-discharge irreversible capacity and the problem of voltage delay phenomenon; Provide the compounded lithium battery of the hard carbon microspheres/expanded graphite of a kind of starch base hard carbon microspheres composite negative pole material; Promote the overall performance of hard carbon cathode material, exploitation function admirable, environmental protection; With low cost, be suitable for the hard carbon cathode material of volume production.
Another object of the present invention provides the preparation method of the hard carbon microspheres composite negative pole material of this lithium battery.
In order to realize the foregoing invention purpose, its concrete technical scheme is following:
The hard carbon microspheres composite negative pole material of a kind of lithium battery; It is characterized in that: by the hard carbon microspheres of starch base and expanded graphite is compound processes, be template with the expanded graphite, the hard carbon microspheres of starch base is inlaid in the middle of the expanded graphite hole; Graphite flake layer relatively easily is enclosed in around the hard carbon microspheres of starch base; Form artificial solid space conductive network, thereby improved the voltage delay phenomenon of hard charcoal negative pole, improved its efficient first.Capacity reaches 440～530mAh/g during this composite material 0.1C discharge, and efficient has reached 77～85% first, and capacity still reaches 420～500mAh/g when big electric current 10C discharges, and has shown good power performance.
The mass ratio of hard carbon microspheres of starch base of the present invention and expanded graphite is 20:1～50:1.
Starch of the present invention comprises cereal starch (like rice starch, cornstarch, sorghum starch, wheaten starch etc.); Potato starch (like tapioca, sweet potato starch, farina etc.), one or more among bean starch (like green starch, broad bean starch, pea starch etc.) and/or other kind of starch (like Tapioca starch, lotus root starch, water chestnut starch, acorn starch).
The preparation method of the hard carbon microspheres negative material of a kind of lithium battery of nucleocapsid structure comprises following processing step:
A, the hard carbon microspheres of preparation starch base;
B, the starch-based carbon microsphere that steps A is obtained and expanded graphite join in the ratio of mass ratio 20:1～50:1 in the non-polar solven of 10～20 times of volumes and obtain solidliquid mixture, and wherein expanded graphite adopts known technology to make or directly buys;
C, the solidliquid mixture that step B is obtained stir or adopt ultrasonic cleaner to shake;
D, adopt centrifugal, filtration or suction filtration mode with solid and separated from solvent, the gained solid is dried in drying box, promptly obtains the hard carbon microspheres of starch base/expanded graphite composite material.
The described method for preparing the hard carbon microspheres of starch base of steps A of the present invention is: starch is joined in the heating furnace; Under inert atmosphere, rise to 100～300 ℃ and heat-treat 1～72h with the heating rate of 0.1～10 ℃/min; Then rising to 700～1500 ℃ with the heating rate of 0.5～30 ℃/min carries out charing to material and handles 0.2～5h; And under inert atmosphere, be cooled to room temperature, obtain starch-based carbon microsphere.
Above-mentioned heating furnace is tube furnace, box type furnace or converter.
Inert atmosphere of the present invention is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
At the non-polar solven described in the step B is ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or xylenes.
Be meant under 20～80 ℃ of temperature in the stirring described in the step C and stir 1～4h with rotating speed 100～1500r/min.
Be meant that in the concussion of the ultrasonic waves for cleaning described in the step C power with rotating speed 200～500w shakes 0.5～2h under 20～40 ℃ of temperature.
Carbon microspheres is dried in drying box described in the step D be meant with carbon microspheres in drying box in 40～80 ℃ the oven dry 2～10 hours.
The useful technique effect that the present invention brings:
Utilize the special construction of graphite and the electric conductivity that conductivity can improve the non-conductor of electricity, graphite normally adds in the electrode material with the form of conductive agent, and the graphite flake layer utilance of this kind technology is obviously lower.If surround electrode material, then can improve the lamella utilance greatly with graphite flake layer.But because graphite layers is merely 0.3354nm apart from less, have only the ion size could insert wherein, the particle of micron level then is difficult to realize effective insertion.Now, the appearance of expanded graphite has solved the problems referred to above, for field of compound material provides comparatively wide research and development space.
1, the initial feed used of this method is a starch, is the recyclable materials that nature extensively exists, and cheap, and the source is abundant, is easy to realize large-scale industrial production;
2, the present invention under inert atmosphere to material through the line stabilization processing, reduced equipment corrosion, and be easy to realize the continued operation of stabilisation, charing;
3, the present invention utilizes the intrinsic pattern of starch material, need not through special balling technique, only uses stabilisation, charing to handle and has promptly obtained the spherical carbon material, and technology is simple;
4, the expanded graphite of the present invention's use is cheap, wide material sources, and economy is far above materials such as the conductive carbon fibre on the market, CNTs;
5, the composite material of the present invention's preparation is owing to have the three-dimensional conductive network that expanded graphite forms, and therefore efficient is higher than the hard charcoal class material of tradition first, and capacity is higher, and high rate performance is good;
6, the present invention utilizes the expanded graphite its specific structure; Carry out compound preparation with the hard carbon microspheres of starch base; Utilize the conduction of building of solid spacial framework that good passage is provided, thereby improve the voltage delay effect of hard raw material of wood-charcoal material, and improve the efficient first of negative material to electronics.
7, the hard carbon cathode material capacity of the present invention's preparation is up to 440～530mAh/g, and about the 350mAh/g far above the conventional graphite negative pole, and high rate performance is good, and can compatible well PC electrolyte.
8, the present invention uses ultrasonic oscillation that two kinds of materials are mixed, and makes the mixing efficiency and the uniformity far above traditional mechanical agitation mode.
Embodiment
Embodiment 1
The hard carbon microspheres composite negative pole material of a kind of lithium battery; It is characterized in that: by the hard carbon microspheres of starch base and expanded graphite is compound processes, be template with the expanded graphite, the hard carbon microspheres of starch base is inlaid in the middle of the expanded graphite hole; Graphite flake layer relatively easily is enclosed in around the hard carbon microspheres of starch base; Form artificial solid space conductive network, thereby improved the voltage delay phenomenon of hard charcoal negative pole, improved its efficient first.Capacity reaches 440mAh/g during this composite material 0.1C discharge, and efficient has reached 77% first, and capacity still reaches 420mAh/g when big electric current 10C discharges, and has shown good power performance; The mass ratio of hard carbon microspheres of described starch base and expanded graphite is 20:1.
The preparation method of the hard carbon microspheres negative material of a kind of lithium battery of nucleocapsid structure comprises following processing step:
A, the hard carbon microspheres of preparation starch base;
B, the starch-based carbon microsphere that steps A is obtained and expanded graphite join in the ratio of mass ratio 20:1 in the non-polar solven of 10 times of volumes and obtain solidliquid mixture, and wherein expanded graphite adopts known technology to make or directly buys;
C, the solidliquid mixture that step B is obtained stir or adopt ultrasonic cleaner to shake;
D, adopt centrifugal, filtration or suction filtration mode with solid and separated from solvent, the gained solid is dried in drying box, promptly obtains the hard carbon microspheres of starch base/expanded graphite composite material.
The method for preparing the hard carbon microspheres of starch base of the present invention is: starch is joined in the heating furnace; Under inert atmosphere, rise to 100 ℃ and heat-treat 1h with the heating rate of 0.1 ℃/min; Then rising to 700 ℃ with the heating rate of 0.5 ℃/min carries out charing to material and handles 0.2h; And under inert atmosphere, be cooled to room temperature, obtain starch-based carbon microsphere.
Above-mentioned heating furnace is tube furnace, box type furnace or converter.
The described inert atmosphere of steps A of the present invention is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
At the non-polar solven described in the step B is ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or xylenes.
Be meant under 20 ℃ of temperature in the stirring described in the step C and stir 1h with rotating speed 100r/min.
Be meant that in the concussion of the ultrasonic waves for cleaning described in the step C power with rotating speed 200w shakes 0.5h under 20 ℃ of temperature.
Carbon microspheres is dried in drying box described in the step D be meant with carbon microspheres in drying box in 40 ℃ the oven dry 2 hours.
Embodiment 2
The hard carbon microspheres composite negative pole material of a kind of lithium battery; It is characterized in that: by the hard carbon microspheres of starch base and expanded graphite is compound processes, be template with the expanded graphite, the hard carbon microspheres of starch base is inlaid in the middle of the expanded graphite hole; Graphite flake layer relatively easily is enclosed in around the hard carbon microspheres of starch base; Form artificial solid space conductive network, thereby improved the voltage delay phenomenon of hard charcoal negative pole, improved its efficient first.Capacity reaches 530mAh/g during this composite material 0.1C discharge, and efficient has reached 85% first, and capacity still reaches 500mAh/g when big electric current 10C discharges, and has shown good power performance; The mass ratio of hard carbon microspheres of described starch base and expanded graphite is 50:1.
The preparation method of the hard carbon microspheres negative material of a kind of lithium battery of nucleocapsid structure comprises following processing step:
A, the hard carbon microspheres of preparation starch base;
B, the starch-based carbon microsphere that steps A is obtained and expanded graphite join in the ratio of mass ratio 50:1 in the non-polar solven of 20 times of volumes and obtain solidliquid mixture, and wherein expanded graphite adopts known technology to make or directly buys;
C, the solidliquid mixture that step B is obtained stir or adopt ultrasonic cleaner to shake;
D, adopt centrifugal, filtration or suction filtration mode with solid and separated from solvent, the gained solid is dried in drying box, promptly obtains the hard carbon microspheres of starch base/expanded graphite composite material.
The method for preparing the hard carbon microspheres of starch base of the present invention is: starch is joined in the heating furnace; Under inert atmosphere, rise to 300 ℃ and heat-treat 72h with the heating rate of 10 ℃/min; Then rising to 1500 ℃ with the heating rate of 30 ℃/min carries out charing to material and handles 5h; And under inert atmosphere, be cooled to room temperature, obtain starch-based carbon microsphere.
Above-mentioned heating furnace is tube furnace, box type furnace or converter.
The described inert atmosphere of steps A of the present invention is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
At the non-polar solven described in the step B is ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or xylenes.
Be meant under 80 ℃ of temperature in the stirring described in the step C and stir 4h with rotating speed 1500r/min.
Be meant that in the concussion of the ultrasonic waves for cleaning described in the step C power with rotating speed 500w shakes 2h under 40 ℃ of temperature.
Carbon microspheres is dried in drying box described in the step D be meant with carbon microspheres in drying box in 80 ℃ the oven dry 10 hours.
Embodiment 3
The hard carbon microspheres composite negative pole material of a kind of lithium battery; It is characterized in that: by the hard carbon microspheres of starch base and expanded graphite is compound processes, be template with the expanded graphite, the hard carbon microspheres of starch base is inlaid in the middle of the expanded graphite hole; Graphite flake layer relatively easily is enclosed in around the hard carbon microspheres of starch base; Form artificial solid space conductive network, thereby improved the voltage delay phenomenon of hard charcoal negative pole, improved its efficient first.Capacity reaches 485mAh/g during this composite material 0.1C discharge, and efficient has reached 81% first, and capacity still reaches 460mAh/g when big electric current 10C discharges, and has shown good power performance; The mass ratio of hard carbon microspheres of described starch base and expanded graphite is 35:1.
The preparation method of the hard carbon microspheres negative material of a kind of lithium battery of nucleocapsid structure comprises following processing step:
A, the hard carbon microspheres of preparation starch base;
B, the starch-based carbon microsphere that steps A is obtained and expanded graphite add in the non-polar solven that is lowered into 15 times of volumes in the ratio of mass ratio 35:1 and obtain solidliquid mixture, and wherein expanded graphite adopts known technology to make or directly buys;
C, the solidliquid mixture that step B is obtained stir or adopt ultrasonic cleaner to shake;
D, adopt centrifugal, filtration or suction filtration mode with solid and separated from solvent, the gained solid is dried in drying box, promptly obtains the hard carbon microspheres of starch base/expanded graphite composite material.
The method for preparing the hard carbon microspheres of starch base of the present invention is: starch is joined in the heating furnace; Under inert atmosphere, rise to 200 ℃ and heat-treat 36.5h with the heating rate of 5 ℃/min; Then rising to 1100 ℃ with the heating rate of 15 ℃/min carries out charing to material and handles 2.6h; And under inert atmosphere, be cooled to room temperature, obtain starch-based carbon microsphere.
Above-mentioned heating furnace is tube furnace, box type furnace or converter.
The described inert atmosphere of steps A of the present invention is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
At the non-polar solven described in the step B is ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or xylenes.
Be meant under 50 ℃ of temperature in the stirring described in the step C and stir 2.5h with rotating speed 800r/min.
Be meant that in the concussion of the ultrasonic waves for cleaning described in the step C power with rotating speed 350w shakes 1.25h under 30 ℃ of temperature.
Carbon microspheres is dried in drying box described in the step D be meant with carbon microspheres in drying box in 60 ℃ the oven dry 6 hours.
Embodiment 4
On the basis of embodiment 1～3; Further; Described starch comprises cereal starch (like rice starch, cornstarch, sorghum starch, wheaten starch etc.); Potato starch (like tapioca, sweet potato starch, farina etc.), one or more among bean starch (like green starch, broad bean starch, pea starch etc.) and/or other kind of starch (like Tapioca starch, lotus root starch, water chestnut starch, acorn starch).
Embodiment 5
A, to get the 50g wheaten starch be raw material; Join among the tube furnace; Under nitrogen atmosphere, rise to 208 ℃ and carry out stabilization processes 46h with the heating rate of 0.2 ℃/min; Then rise to 1100 ℃ and material is carried out charing handle 2h, and under inert atmosphere, be cooled to room temperature, obtain the wheaten starch based carbon microsphere with the heating rate of 3 ℃/min; Use general known method to prepare expanded graphite; Get hard carbon microspheres of 10g and 0.5g expanded graphite, join in the 50ml ethanol, under 60 ℃ of temperature, stir, dipping 1.5h with rotating speed 150r/min; Adopt centrifugal mode with solid and separated from solvent, with solid in drying box 40 ℃ the oven dry 10h, promptly obtain the hard carbon microspheres of starch base/expanded graphite composite material.
B, getting the 1g composite material that step 1 makes, is that 92:3:2.5:2.5 evenly mixes with conductive black, sodium cellulose glycolate and butadiene-styrene rubber by mass ratio, sizes mixing, and on the long-pending electric body of Copper Foil, films, and is prepared into the negative electricity pole piece.Be to electrode with metal lithium sheet again, 1mol/L LiPF
6The EC/DMC/EMC mixed liquor be electrolyte (wherein the mass ratio of EC:DMC:EMC is 1:1:1), the Celgard2400 polypropylene film is a barrier film, is assembled into the button simulated battery.Record this negative material under the condition of charge-discharge velocity 0.1C first reversible capacity reach 460mAh/g, efficient is 84% first.Reversible capacity reaches 433mAh/g under the condition of discharge rate 10C.
Embodiment 6
A, to get the 150g farina be raw material; Join among the box type furnace; Under nitrogen atmosphere, rise to 300 ℃ and carry out stabilization processes 16h with the heating rate of 0.1 ℃/min; Then rise to 1000 ℃ and material is carried out charing handle 1h, and under inert atmosphere, be cooled to room temperature, obtain the farina based carbon microsphere with the heating rate of 20 ℃/min; Use general known method to prepare expanded graphite; Get hard carbon microspheres of 30g and 1g expanded graphite, join in the 100ml acetone, the ultrasonic power with 200w under 40 ℃ of temperature shakes 1.5h; The mode that adopts suction filtration is solid and separated from solvent, with the solid of institute in drying box 80 ℃ dry 1h, promptly obtain the hard carbon microspheres of starch base/expanded graphite composite material.
B, getting the 2g composite material that step 1 makes, is that 92:3:2.5:2.5 evenly mixes with conductive black, sodium cellulose glycolate and butadiene-styrene rubber by mass ratio, sizes mixing, and on the long-pending electric body of Copper Foil, films, and is prepared into the negative electricity pole piece.Be to electrode with metal lithium sheet again, 1mol/L LiPF
6The EC/DMC/EMC mixed liquor be electrolyte (wherein the mass ratio of EC:DMC:EMC is 1:1:1), the Celgard2400 polypropylene film is a barrier film, is assembled into the button simulated battery.Record this negative material under the condition of charge-discharge velocity 0.1C first reversible capacity reach 530mAh/g, efficient is 78% first.Reversible capacity reaches 500mAh/g under the condition of discharge rate 10C.
Embodiment 7
A, to get the 3000g pea starch be raw material; Join among the converter; Under argon gas atmosphere, rise to 250 ℃ and carry out stabilization processes 30h with the heating rate of 1 ℃/min; Then rise to 1500 ℃ and material is carried out charing handle 5h, and under inert atmosphere, be cooled to room temperature, obtain the pea starch based carbon microsphere with the heating rate of 10 ℃/min; Use general known method to prepare expanded graphite; Get hard carbon microspheres of 20g and 1g expanded graphite, join in the 50ml toluene, under 80 ℃ of temperature, stir, dipping 4h with rotating speed 1500r/min; Adopt centrifugal mode with solid and separated from solvent, with solid in drying box 80 ℃ the oven dry 2h, promptly obtain the hard carbon microspheres of starch base/expanded graphite composite material.
B, getting the 8g composite material that step 1 makes, is that 92:3:2.5:2.5 evenly mixes with conductive black, sodium cellulose glycolate and butadiene-styrene rubber by mass ratio, sizes mixing, and on the long-pending electric body of Copper Foil, films, and is prepared into the negative electricity pole piece.Be to electrode with metal lithium sheet again, 1mol/L LiPF
6The EC/DMC/EMC mixed liquor be electrolyte (wherein the mass ratio of EC:DMC:EMC is 1:1:1), the Celgard2400 polypropylene film is a barrier film, is assembled into the button simulated battery.Record this negative material under the condition of charge-discharge velocity 0.1C first reversible capacity reach 440mAh/g, efficient is 85% first.Reversible capacity reaches 420mAh/g under the condition of discharge rate 10C.
Claims (10)
1. hard carbon microspheres composite negative pole material of lithium battery; It is characterized in that: by the hard carbon microspheres of starch base and expanded graphite is compound processes; With the expanded graphite is template, and the hard carbon microspheres of starch base is inlaid in the middle of the expanded graphite hole, and graphite flake layer is enclosed in around the hard carbon microspheres of starch base; Form artificial solid space conductive network; Capacity reaches 440～530mAh/g during this composite material 0.1C discharge, and efficient has reached 77～85% first, and capacity still reaches 420～500mAh/g when 10C discharges.
2. the hard carbon microspheres composite negative pole material of a kind of lithium battery according to claim 1 is characterized in that: the mass ratio of hard carbon microspheres of starch base and expanded graphite is 20:1～50:1.
3. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 1 is characterized in that: comprise following processing step:
A, the hard carbon microspheres of preparation starch base;
B, the starch-based carbon microsphere that steps A is obtained and expanded graphite join in the ratio of mass ratio 20:1～50:1 in the non-polar solven of 10～20 times of volumes and obtain solidliquid mixture;
C, the solidliquid mixture that step B is obtained stir or adopt ultrasonic cleaner to shake;
D, adopt centrifugal, filtration or suction filtration mode with solid and separated from solvent, the gained solid is dried in drying box, promptly obtains the hard carbon microspheres of starch base/expanded graphite composite material.
4. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 3; It is characterized in that: the method for preparing the hard carbon microspheres of starch base described in the steps A is: starch is joined in the heating furnace; Under inert atmosphere, rise to 100～300 ℃ and heat-treat 1～72h with the heating rate of 0.1～10 ℃/min; Then rising to 700～1500 ℃ with the heating rate of 0.5～30 ℃/min carries out charing to material and handles 0.2～5h; And under inert atmosphere, be cooled to room temperature, obtain starch-based carbon microsphere.
5. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 4, it is characterized in that: described heating furnace is tube furnace, box type furnace or converter.
6. according to the preparation method of the hard carbon microspheres negative material of lithium battery of claim 3 or 4 described a kind of nucleocapsid structures, it is characterized in that: described inert atmosphere is nitrogen atmosphere, argon gas atmosphere or helium atmosphere.
7. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 3, it is characterized in that: at the non-polar solven described in the step B is ethanol, acetone, toluene, n-hexane, cyclohexane, benzene or xylenes.
8. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 3 is characterized in that: be meant under 20～80 ℃ of temperature in the stirring described in the step C and stir 1～4h with rotating speed 100～1500r/min.
9. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 3 is characterized in that: be meant that in the concussion of the ultrasonic waves for cleaning described in the step C power with rotating speed 200～500w shakes 0.5～2h under 20～40 ℃ of temperature.
10. the preparation method of the hard carbon microspheres negative material of the lithium battery of a kind of nucleocapsid structure according to claim 3 is characterized in that: be meant carbon microspheres is dried in drying box described in the step D carbon microspheres was dried 2～10 hours in 40～80 ℃ in drying box.
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| CN102881883A (en) * | 2012-10-17 | 2013-01-16 | 中国东方电气集团有限公司 | Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material |
| CN102903952A (en) * | 2012-10-17 | 2013-01-30 | 中国东方电气集团有限公司 | Lithium ion battery adopting ternary composite cathode material and preparation method thereof |
| CN103647082A (en) * | 2013-12-24 | 2014-03-19 | 中国船舶重工集团公司第七一二研究所 | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material |
| CN103996833A (en) * | 2014-06-12 | 2014-08-20 | 上海第二工业大学 | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material |
| CN107425215A (en) * | 2016-05-23 | 2017-12-01 | 宁波杉杉新材料科技有限公司 | A kind of Preparation method and use of starch base composite hard carbon cathode material |
| CN111525123A (en) * | 2020-04-29 | 2020-08-11 | 国家纳米科学中心 | Cathode material of water-based lithium ion battery and preparation method and application thereof |
| CN112531160A (en) * | 2019-09-19 | 2021-03-19 | 贝特瑞新材料集团股份有限公司 | Amorphous carbon negative electrode material and preparation method and application thereof |
| CN112713277A (en) * | 2020-12-30 | 2021-04-27 | 宁波杉杉新材料科技有限公司 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
| CN115448307A (en) * | 2022-09-13 | 2022-12-09 | 季华实验室 | Expanded graphite-based carbon composite material and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881883A (en) * | 2012-10-17 | 2013-01-16 | 中国东方电气集团有限公司 | Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material |
| CN102903952A (en) * | 2012-10-17 | 2013-01-30 | 中国东方电气集团有限公司 | Lithium ion battery adopting ternary composite cathode material and preparation method thereof |
| CN102881883B (en) * | 2012-10-17 | 2015-06-03 | 中国东方电气集团有限公司 | Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material |
| CN102903952B (en) * | 2012-10-17 | 2015-07-08 | 中国东方电气集团有限公司 | Lithium ion battery adopting ternary composite cathode material and preparation method thereof |
| CN103647082A (en) * | 2013-12-24 | 2014-03-19 | 中国船舶重工集团公司第七一二研究所 | Preparation method of lithium ion secondary battery hard-carbon microsphere negative electrode material |
| CN103647082B (en) * | 2013-12-24 | 2016-05-04 | 中国船舶重工集团公司第七一二研究所 | The preparation method of the hard carbon microsphere cathode material of a kind of lithium rechargeable battery |
| CN103996833A (en) * | 2014-06-12 | 2014-08-20 | 上海第二工业大学 | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material |
| CN107425215A (en) * | 2016-05-23 | 2017-12-01 | 宁波杉杉新材料科技有限公司 | A kind of Preparation method and use of starch base composite hard carbon cathode material |
| CN112531160A (en) * | 2019-09-19 | 2021-03-19 | 贝特瑞新材料集团股份有限公司 | Amorphous carbon negative electrode material and preparation method and application thereof |
| CN111525123A (en) * | 2020-04-29 | 2020-08-11 | 国家纳米科学中心 | Cathode material of water-based lithium ion battery and preparation method and application thereof |
| CN112713277A (en) * | 2020-12-30 | 2021-04-27 | 宁波杉杉新材料科技有限公司 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
| CN115448307A (en) * | 2022-09-13 | 2022-12-09 | 季华实验室 | Expanded graphite-based carbon composite material and preparation method and application thereof |
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