CN103094528A - Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material - Google Patents
Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material Download PDFInfo
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Abstract
The invention relates to a preparation method of a hard carbon cathode material. The preparation method comprises the step of preparing the hard carbon cathode material by using thermosetting resin or pyrolysis products of a mixture of thermosetting resin and thermoplastic resin as a hard carbon matrix and adopting a carbon material as a coating. In the preparation process of the hard carbon cathode material, a curing agent and a doping matter can be added. The hard carbon cathode material prepared by adopting the preparation method has the characteristics of high capacity, high first-time coulombic efficiency, excellent rate performance, low cost and the like, and is suitable for industrialized production.
Description
Technical field
The present invention relates to the lithium ion battery negative material field, particularly, the present invention relates to hard carbon cathode material and preparation method thereof for a kind of lithium ion power and energy-storage battery.
Background technology
Along with scientific and technological development and growth in the living standard, the mankind increase day by day to the demand of the equipment such as multifunctional portable electronic equipment and electric motor car, and the new type lithium ion battery electrode material that therefore study that energy density is high, load characteristic good, discharge and recharge fast, security performance is high, have extended cycle life, cost is low has become important in the world Disciplinary Frontiers.Negative material is one of key factor affected capacity of lithium ion battery, and in prior art, general employing is the graphite of graphite or modification.Yet its theoretical embedding lithium capacity 372mAh/g more and more can not satisfy the demands, and distinctive layer structure causes the cyclical stability of limited number of time, also extremely sensitive to electrolyte, therefore needs the negative material of finding a kind of alternative graphite badly.
Hard carbon is a kind of of material with carbon element, it has, and specific capacity is high, the characteristic such as large, the good rate capability of irreversible capacity first, there is excellent multiplying power and cycle performance and low-temperature characteristics simultaneously, but the hard carbon initial negative material used that is lithium ion battery, as furfural resin thermal decomposition product, phenolic resins thermal decomposition product, carbon black etc., have a reversible capacity low, efficiency is low first, the shortcomings such as discharge voltage is low, therefore, need to carry out modification to hard carbon material.
CN101887966B discloses a kind of preparation method of composite hard carbon cathode material of lithium ion battery, comprise: solidify, pyrolysis, pulverizing, coating, compared with prior art, utilization is added curing agent and alloy and is cured and does carbon source in resin, through pyrolysis, coating, obtain composite hard carbon cathode material, but the method adopts thermoplastic resin, be raw material, cost is higher, and the electric property of the negative material obtained can not be satisfied the demand.
Therefore, provide a kind of low cost, and the hard carbon cathode material of electric property excellence is the technical barrier in affiliated field.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of lithium ion power and the energy-storage battery preparation method of hard carbon cathode material.
The technical problem to be solved in the present invention is to reduce the cell negative electrode material cost, improves first charge-discharge enclosed pasture efficiency, high-rate charge-discharge capability and the high low temperature cycle performance of cell negative electrode material.
The preparation method of described hard carbon cathode material comprises: the thermal decomposition product of mixture of thermosetting resin or thermosetting resin and thermoplastic resin of take is the hard carbon matrix, and adopting material with carbon element is that coating obtains hard carbon cathode material.
Preferably, described material with carbon element is obtained by the pyrolysis of coating presoma.
Preferably, the preparation method of described hard carbon cathode material comprises the following steps:
(1) the hard carbon matrix precursor is solidified, obtain solid precursor, wherein, described hard carbon matrix precursor contains resin, the mixture that described resin is thermosetting resin or thermosetting resin and thermoplastic resin, and thermoplastic resin is 0～90% of resin gross mass;
(2) solid precursor step (1) obtained carries out pyrolysis, obtains the hard carbon matrix;
(3) hard carbon matrix step (2) obtained mixes with the coating presoma, and pyrolysis, obtain hard carbon cathode material, and the mass ratio of wherein said coating presoma and hard carbon matrix precursor is 0.8:100 ~ 50:100.
Described thermoplastic resin be the resin gross mass 0% the time, mean described hard carbon matrix precursor containing thermoplastic resin.
Preferably, step (1) comprising: precuring after resin is mixed with alloy, and fragmentation, mix with curing agent, obtain the hard carbon matrix precursor, then solidify, obtain solid precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, thermoplastic resin is 0～90% of resin gross mass, and described alloy is 0 ~ 20% of described hard carbon matrix precursor gross mass, and described curing agent is 0 ~ 90% of described hard carbon matrix precursor gross mass; Preferably, describedly be mixed into stirring; Preferably, described mixing speed is 1000～3500r/min, and more preferably 1100～3000r/min, be particularly preferably 1200～2800r/min; Preferably, described incorporation time is at least 15 minutes, more preferably 20 ~ 100 minutes, is particularly preferably 30 ~ 120 minutes.
Preferably, step (1) comprising: resin is mixed with alloy and/or curing agent, obtain the hard carbon matrix precursor, then solidify, obtain solid precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, thermoplastic resin is 0～90% of resin gross mass, and described alloy is 0 ~ 20% of described hard carbon matrix precursor gross mass, and described curing agent is 0 ~ 90% of described hard carbon matrix precursor gross mass; Preferably, describedly be mixed into stirring; Preferably, described mixing speed is 1000～5000r/min, and more preferably 1100～4800r/min, be particularly preferably 1200～4400r/min; Preferably, described incorporation time is at least 15 minutes, more preferably 20 ~ 100 minutes, is particularly preferably 30 ~ 120 minutes.
Preferably, step (1) comprising: by resin solidification, obtain solid precursor, then with alloy, mix, obtain the hard carbon matrix precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, thermoplastic resin is 0～90% of resin gross mass, and described alloy is 0 ~ 20% of described hard carbon matrix precursor gross mass; Preferably, describedly be mixed into stirring; Preferably, described mixing speed is 1000～3500r/min, and more preferably 1100～3000r/min, be particularly preferably 1200～2800r/min; Preferably, described incorporation time is at least 15 minutes, more preferably 20 ~ 100 minutes, is particularly preferably 30 ~ 120 minutes.
Described hard carbon matrix precursor can comprise according to mass percent: 10 ~ 100% resin and 0 ~ 90% curing agent; Also can comprise: 10 ~ 100% resin, 0 ~ 20% alloy, 0 ~ 90% curing agent; Also can comprise: 80 ~ 100% resin and 0 ~ 20% alloy; Wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, and thermoplastic resin is 0～90% of resin gross mass.
Preferably, described thermosetting resin is furfural phenol resin, furfuryl alcohol resin, polybutadiene, melamine resin, epoxy resin, phenolic resins, 1 kind or the combination of at least 2 kinds in polyurethane and Lauxite, the typical but non-limiting example of described combination comprises the combination of furfural phenol resin and furfuryl alcohol resin, the combination of polybutadiene and melamine resin, epoxy resin, the combination of phenolic resins and polyurethane, phenolic resins, the combination of polyurethane and Lauxite, furfuryl alcohol resin, polybutadiene, the combination of melamine resin and epoxy resin, melamine resin, epoxy resin, phenolic resins, the combination of polyurethane and Lauxite etc.
Preferably, described thermoplastic resin is acrylic resin, Merlon, polyvinyl chloride, polyurethane, 1 kind or the combination of at least 2 kinds in polyformaldehyde, the typical but non-limiting example of described combination comprises the combination of acrylic resin and Merlon, the combination of acrylic resin and polyvinyl chloride, the combination of polyurethane and polyformaldehyde, the combination of polyvinyl chloride and polyurethane, Merlon, the combination of polyvinyl chloride and polyurethane, polyvinyl chloride, the combination of polyurethane and acetal resin, acrylic resin, Merlon, polyvinyl chloride, the combination of polyurethane and polyformaldehyde etc.
Preferably, described coating presoma is the ethyl-methyl carbonic ester, butadiene-styrene rubber, citric acid, epoxy resin, phenolic resins, pitch, poly(ethylene oxide), PPOX, polyimides, polypyrrole, polyaniline, the polyethylene glycol imines, poly m-phenylene diamine, polythiophene, polyacrylonitrile, polytetrafluoroethylene, Kynoar, polyphenylene sulfide, 1 kind or the combination of at least 2 kinds in polymethyl methacrylate and poly-phenylene vinylene (ppv), the typical but non-limiting example of described combination comprises the combination of ethyl-methyl carbonic ester and butadiene-styrene rubber, the combination of polyimides and polypyrrole, the combination of polyethylene glycol imines and poly m-phenylene diamine, citric acid, the combination of epoxy resin and phenolic resins, pitch, the combination of poly(ethylene oxide) and PPOX, polyimides, polypyrrole, the combination of polyaniline and polyethylene glycol imines, poly m-phenylene diamine, polythiophene, the combination of polyacrylonitrile and polytetrafluoroethylene, Kynoar, the polyethylene glycol imines, polyphenylene sulfide, the combination of polymethyl methacrylate and poly-phenylene vinylene (ppv), phenolic resins, pitch, poly(ethylene oxide), PPOX, the combination of polyimides and polypyrrole etc.
Preferably, described alloy is a kind or the combination of at least 2 kinds in metal simple-substance, non-metal simple-substance, metallic compound and nonmetallic compound, preferably, described metal simple-substance is a kind or the combination of at least 2 kinds in copper, iron, nickel, cobalt, manganese, titanium, vanadium, chromium, tin and antimony, preferably, described metallic compound is metal oxide, metal hydroxides, metal phosphate, the metal tripolyphosphate hydrogen salt, 1 kind or the combination of at least 2 kinds in metal halide and metal acetate, nickel oxide more preferably, cobalt oxide, tin ash, manganese dioxide, titanium dioxide, vanadic oxide, mangano-manganic oxide, di-iron trioxide, chrome green, Kocide SD, nickel hydroxide, cobalt hydroxide, sodium phosphate, sodium dihydrogen phosphate, 1 kind or the combination of at least 2 kinds in stannic chloride and tin acetate, be particularly preferably nickel oxide, cobalt oxide, Kocide SD, nickel hydroxide, cobalt hydroxide, sodium phosphate, sodium dihydrogen phosphate, 1 kind or the combination of at least 2 kinds in stannic chloride and tin acetate, preferably, described non-metal simple-substance is a kind or the combination of at least 2 kinds in boron, phosphorus, silicon and sulphur, is particularly preferably a kind or the combination of at least 2 kinds in boron, silicon and sulphur, preferably, described nonmetallic compound is a kind or the combination of at least 2 kinds in borate, boric acid, borate, silicic acid, silicate, esters of silicon acis, Si oxide, phosphate, phosphate, phosphoric acid, phosphorous oxides, sulfuric acid and sulfate, is particularly preferably a kind or the combination of at least 2 kinds in boric acid, glycol borate, silicon boride, boron chloride, silicon dioxide, silicic acid, organic siliconresin, ammonium sulfate, phosphorus pentoxide, phosphoric acid, ammonium phosphate, phosphoric acid dihydro amine.
Described curing agent can be selected as required by one of ordinary skill in the art; Preferably, described curing agent is a kind or the combination of at least 2 kinds in m-phenylene diamine (MPD), aniline, hexamethylene diamine, melamine, melamine resin, benzene sulfonic acid, hexamethylenetetramine, polyamide and phthalic anhydride.
The content of described thermoplastic resin can be 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 84%, 86%, 87%, 89% etc. of described resin gross mass; Preferably, described thermoplastic resin is 0～88% of resin gross mass, is particularly preferably 0 ~ 85%.
The content of described alloy can be 0.1%, 0.2%, 0.3%, 0.5%, 1%, 2%, 3%, 5%, 7%, 9%, 11%, 14%, 16%, 17%, 19% etc. of described hard carbon matrix precursor gross mass; Preferably, described alloy is 0 ~ 18% of described hard carbon matrix precursor gross mass, is particularly preferably 0 ~ 15%.
The content of described curing agent can be 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 84%, 86%, 87%, 89% etc. of described hard carbon matrix precursor gross mass; Preferably, described curing agent is 0 ~ 88% of described hard carbon matrix precursor gross mass, is particularly preferably 0 ~ 85%.
Preferably, described being solidificated in air of step (1) carried out.
Preferably, the described curing temperature of step (1) is 70 ~ 300 ℃, more preferably 75 ~ 280 ℃, is particularly preferably 80 ~ 250 ℃.
Preferably, step (1) described curing time is at least 0.5 hour, such as 0.6 hour, 0.7 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 10 hours, 20 hours, 40 hours, 50 hours, 59 hours, 61 hours, 70 hours, 79 hours, 81 hours, 85 hours, 90 hours etc., more preferably 0.8 ~ 80 hour, more preferably 1 ~ 60 hour, be particularly preferably 1 ~ 24 hour.
Preferably, the described precuring of step (1) is carried out in air.
Preferably, the described precuring temperature of step (1) is 70 ~ 300 ℃, more preferably 75 ~ 280 ℃, is particularly preferably 80 ~ 250 ℃.
Preferably, the described precuring time of step (1) is at least 0.5 hour, such as 0.6 hour, 0.7 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 10 hours, 20 hours, 40 hours, 50 hours, 59 hours, 61 hours, 70 hours, 80 hours, 85 hours, 90 hours etc., more preferably 0.8 ~ 60 hour, be particularly preferably 1 ~ 40 hour.
Preferably, the product of the described precuring of step (1) is carried out to fragmentation; Preferably, described mechanical crushing or the ball milling of being broken for; Preferably, described broken terminal is particle diameter 2～50 μ m.
Preferably, the described pyrolysis temperature of step (2) is 500 ~ 1350 ℃, more preferably 550 ~ 1300 ℃, is particularly preferably 580 ~ 1200 ℃.
Preferably, reach heating rate before the described pyrolysis temperature of step (2) and be 20 ℃/below min, such as 0.1 ℃/min, 0.2 ℃/min, 0.4 ℃/min, 0.6 ℃/min, 1 ℃/min, 2 ℃/min, 5 ℃/min, 7 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 14 ℃/min, 16 ℃/min, 18 ℃/min, 19 ℃/min etc., more preferably 15 ℃/below min, be particularly preferably 0.5 ~ 8 ℃/min.
Preferably, the described pyrolysis time of step (2) is at least 0.3 hour, such as 0.4 hour, 0.55 hour, 0.7 hour, 1 hour, 2 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 11 hours, 15 hours, 20 hours etc., more preferably 0.5 ~ 10 hour, be particularly preferably 0.6 ~ 7.2 hour.
Preferably, the described pyrolysis of step (2) is carried out under inert gas shielding; Preferably, described inert gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton and xenon, is particularly preferably nitrogen; Preferably, described inert gas flow is 0.1～1.2m
3/ h, more preferably 0.14～1m
3/ h, be particularly preferably 0.18～0.88m
3/ h.
Preferably, naturally be cooled to room temperature after the described pyrolysis of step (2).
Preferably, hard carbon matrix step (2) obtained carries out fragmentation; Preferably, described mechanical crushing or the ball milling of being broken for; Preferably, described broken terminal is particle diameter 2～50 μ m.
Preferably, the mass ratio of described coating presoma and hard carbon matrix precursor is 1:100 ~ 45:100, is particularly preferably 1.2:100 ~ 40:100.
Preferably, step (3) is described is mixed into stirring; Preferably, described mixing speed is 1200～4000r/min, and more preferably 1400～3500r/min, be particularly preferably 1500～3300r/min.
Preferably, the described incorporation time of step (3) is at least 15 minutes, more preferably 20 ~ 55 minutes, is particularly preferably 28 ~ 48 minutes.
Preferably, the described pyrolysis temperature of step (3) is 700 ~ 1550 ℃, more preferably 750 ~ 1500 ℃, is particularly preferably 800 ~ 1400 ℃.
Preferably, reach heating rate before the described pyrolysis temperature of step (3) and be 20 ℃/below min, such as 0.1 ℃/min, 0.2 ℃/min, 0.4 ℃/min, 0.6 ℃/min, 1 ℃/min, 2 ℃/min, 5 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 14 ℃/min, 16 ℃/min, 18 ℃/min, 19 ℃/min etc., more preferably 12 ℃/below min, be particularly preferably 1.2 ~ 7.2 ℃/min.
Preferably, the described pyrolysis time of step (3) is at least 0.3 hour, such as 0.4 hour, 0.55 hour, 0.7 hour, 1.5 hours, 2.5 hours, 5 hours, 6 hours, 7 hours, 8.5 hours, 9 hours, 11 hours, 15 hours, 20 hours etc., more preferably 1 ~ 10 hour, be particularly preferably 2 ~ 8 hours.
Preferably, naturally be cooled to room temperature after the described pyrolysis of step (3).
Preferably, the described pyrolysis of step (3) is carried out under inert gas shielding; Preferably, described inert gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton and xenon, is particularly preferably nitrogen; Preferably, described inert gas flow is 0.1～1.2m
3/ h, more preferably 0.14～1m
3/ h, be particularly preferably 0.18～0.88m
3/ h.
Preferably, the preparation method of described hard carbon cathode material comprises the following steps:
(1) by mass percentage by 80 ~ 100% resin and 0 ~ 20% alloy, at rotating speed, be under 1500～5000r/min, stir at least 15min to evenly, solidify at least 0.5h in air, under 70 ~ 300 ℃, obtain solid-state precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, and thermoplastic resin is 0～90% of resin gross mass;
(2) the following heating rate to 500 ~ 1350 ℃ with 20 ℃/min, pyrolysis is 0.3h at least, naturally is cooled to room temperature, then carries out fragmentation, and obtaining granularity is the hard carbon matrix of 2～50 μ m;
(3) add the coating presoma in the hard carbon matrix, rotating speed with 1200～4000r/min mixes at least 15min, then the following heating rate to 700 ~ 1550 ℃ with 20 ℃/min, time is 0.3h at least, carry out the coating pyrolysis processing, naturally be cooled to room temperature, obtain the lithium ion battery hard carbon cathode material, the mass ratio of wherein said coating presoma and hard carbon matrix precursor is 0.8:100 ~ 50:100.
Described alloy is liquid state or solid particle, has and improves low-cost lithium ion power of the present invention and hard carbon cathode material capacity and the effect of enclosed pasture efficiency first for energy-storage battery.Described curing agent is for improving the capacity of hard carbon, enclosed pasture efficiency and productive rate first.Adopt conventional thermosetting resin and thermoplastic resin, metal simple-substance, non-metal simple-substance, metallic compound or nonmetallic compound, curing agent, coating, of the present invention the cost of material is low.
One of purpose of the present invention is to provide a kind of hard carbon cathode material prepared by described method.Described hard carbon cathode material is shaped as irregular block fine particle, and particle size range is 0.8～82 μ m, has pore structure, and aperture is 0.5～80nm, and porosity is 10～17%, and specific area is 1.92～72.0m
2/ g, crystal layer spacing d
002be 0.341～0.472nm, real density is 1.58～2.32g/cm
3, tap density is 0.89～1.42g/cm
3, the content of its C element is higher than 90.6%.
Compared with prior art, adopting the mixture of thermosetting resin or thermosetting resin and thermoplastic resin is raw material in the present invention, and cost is lower, effectively improves the cycle performance of negative material, the negative material excellent performance prepared; Simultaneously, in one embodiment, adopt the mode of precuring can improve yield.As preferred technical scheme, by adding in the mixture at thermosetting resin and thermoplastic resin after alloy and curing agent as carbon source, after through Pintsch process and coating, obtain low-cost hard carbon cathode material.Hard carbon cathode material prepared by the method for the invention is when 0.2C, and reversible capacity is more than 464.8mAh/g first, and enclosed pasture efficiency is more than 80.2% first, have capacity high, first the enclosed pasture efficiency large, the high rate performance excellence, the characteristics such as cost is low, suitability for industrialized production.
The accompanying drawing explanation
The stereoscan photograph of the negative material that Fig. 1 is the embodiment of the present invention 1 preparation.
The XRD figure of the negative material that Fig. 2 is the embodiment of the present invention 1 preparation.
The Raman spectrogram of the negative material that Fig. 3 is the embodiment of the present invention 1 preparation.
Initial charge performance chart under the different multiplying of the negative material that Fig. 4 is the embodiment of the present invention 1 preparation.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
(1) precuring: add 15g alloy phosphoric acid dihydro amine in the 60g furfural phenol resin, adopt high speed dispersor, rotating speed is 2800r/min, and the time is 30min, in air, under 250 ℃, solidifies 4h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 20 μ m.
(3) solidify: add the curing agent hexamethylene diamine of 25g in powder, stir, in air, under 200 ℃, solidify 12h, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 1050 ℃ of 10 ℃/min, pyrolysis 1h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.3m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 18 μ m, obtains the hard carbon matrix.
(6) coat: add 24g coating presoma epoxy resin in the hard carbon matrix; in the VC mixer; rotating speed mixing 50min with 1500r/min; then put into chamber type electric resistance furnace; with the heating rate to 1200 ℃ of 2 ℃/min, insulation 4h, processed; under nitrogen protection, carry out, nitrogen flow is 0.3m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 2
(1) precuring: add 10g alloy phosphoric acid in 80g phenolic resins, adopt high speed dispersor, rotating speed is 2000r/min, and the time is 60min, in air, under 200 ℃, solidifies 6h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 24 μ m.
(3) solidify: add the curing agent melamine of 10g in powder, stir, in air, under 220 ℃, solidify 6h, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 950 ℃ of 5 ℃/min, pyrolysis 2h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.4m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 10 μ m, obtains the hard carbon matrix.
(6) coat: add 28g coating presoma polymethyl methacrylate in the hard carbon matrix; in the VC mixer; rotating speed mixing 40min with 1800r/min; then put into chamber type electric resistance furnace; with the heating rate to 1200 ℃ of 5 ℃/min, insulation 3h, processed; under nitrogen protection, carry out, nitrogen flow is 0.4m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 3
(1) precuring: add 15g alloy boric acid in 70g epoxy resin, adopt high speed dispersor, rotating speed is 1200r/min, and the time is 120min, in air, under 150 ℃, solidifies 8h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 22 μ m.
(3) solidify: add the curing agent phthalic anhydride of 15g in powder, stir, in air, under 80 ℃, solidify 20h, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 950 ℃ of 12 ℃/min, pyrolysis 1h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.4m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 16 μ m, obtains the hard carbon matrix.
(6) coat: add 10g coating presoma aniline in the hard carbon matrix; in the VC mixer; rotating speed mixing 60min with 2000r/min; then put into chamber type electric resistance furnace; with the heating rate to 1200 ℃ of 7 ℃/min, insulation 4h, processed; under nitrogen protection, carry out, nitrogen flow is 0.3m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 4
(1) precuring: add 15g alloy stannic hydroxide in the 50g melamine resin, adopt high speed dispersor, rotating speed is 1500r/min, and the time is 90min, in air, under 100 ℃, solidifies 12h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 24 μ m.
(3) solidify: add the curing agent aniline of 35g in powder, stir, in air, under 100 ℃, solidify 12h, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 800 ℃ of 5 ℃/min, pyrolysis 3h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.3m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 16 μ m, obtains the hard carbon matrix.
(6) coat: add 18g coating presoma citric acid in the hard carbon matrix; in the VC mixer; rotating speed mixing 60min with 2400r/min; then put into chamber type electric resistance furnace; with the heating rate to 1000 ℃ of 6 ℃/min, insulation 3h, processed; under nitrogen protection, carry out, nitrogen flow is 0.8m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 5
(1) precuring: add 12g alloy glass putty in the 60g furfuryl alcohol resin, adopt high speed dispersor, rotating speed is 1800r/min, and the time is 70min, in air, under 180 ℃, solidifies 8h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 30 μ m.
(3) solidify: add the curing agent m-phenylene diamine (MPD) of 28g in powder, stir, in air, under 160 ℃, solidify 15h, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 1200 ℃ of 16 ℃/min, pyrolysis 4h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.2m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 19 μ m, obtains the hard carbon matrix.
(6) coat: add 10g coating presoma poly-phenylene vinylene (ppv) in the hard carbon matrix; in the VC mixer; rotating speed mixing 40min with 2600r/min; then put into chamber type electric resistance furnace; with the heating rate to 1300 ℃ of 4 ℃/min, insulation 5h, processed; under nitrogen protection, carry out, nitrogen flow is 0.6m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 6
(1) precuring: add 10g alloy ammonium phosphate in the 70g polybutadiene, adopt high speed dispersor, rotating speed is 1500r/min, and the time is 110min, in air, under 230 ℃, solidifies 4h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 22 μ m.
(3) solidify: add the curing agent m-phenylene diamine (MPD) of 20g in powder, stir, in air, under 90 ℃, solidify 20h, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 1100 ℃ of 4 ℃/min, pyrolysis 2h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.8m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 20 μ m, obtains the hard carbon matrix.
(6) coat: add 8g coating presoma butadiene-styrene rubber in the hard carbon matrix; in the VC mixer; rotating speed mixing 65min with 1900r/min; then put into chamber type electric resistance furnace; with the heating rate to 1100 ℃ of 5 ℃/min, insulation 4h, processed; under nitrogen protection, carry out, nitrogen flow is 0.4m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 7
(1) solidify: add 20g alloy stannic chloride in the mixture of 60g polyurethane and 20g furfuryl alcohol resin, adopt high speed dispersor, rotating speed is 1200r/min, and the time is 100min, in air, under 160 ℃, solidifies 9h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 35 μ m.
(3) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 900 ℃ of 10 ℃/min, pyrolysis 5h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.8m
3/ h.
(4) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 25 μ m, obtains the hard carbon matrix.
(5) coat: add 34g coating presoma PPOX in the hard carbon matrix; in the VC mixer; rotating speed mixing 60min with 1800r/min; then put into chamber type electric resistance furnace; with the heating rate to 1100 ℃ of 5 ℃/min, insulation 3h, processed; under nitrogen protection, carry out, nitrogen flow is 0.6m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 8
(1) solidify: the mixture of 40g Lauxite and 60g phenolic resins in air, solidify 24h under 85 ℃, is obtained to the precuring presoma.
(2) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 1000 ℃ of 8 ℃/min, pyrolysis 6h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.6m
3/ h.
(3) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 20 μ m, obtains the hard carbon matrix.
(4) coat: add 12g coating presoma polypyrrole in the hard carbon matrix; in the VC mixer; rotating speed mixing 55min with 2200r/min; then put into chamber type electric resistance furnace; with the heating rate to 1000 ℃ of 7 ℃/min, insulation 4h, processed; under nitrogen protection, carry out, nitrogen flow is 0.3m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 9
(1) solidify: add 45g curing agent hexamethylenetetramine in the 55g furfuryl alcohol resin, adopt high speed dispersor, rotating speed is 4400r/min, and the time is 20min, in air, under 85 ℃, solidifies 30h, obtains the precuring presoma.
(2) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 800 ℃ of 6 ℃/min, pyrolysis 6h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.4m
3/ h.
(3) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 24 μ m, obtains the hard carbon matrix.
(4) coat: add 15g coating presoma polyaniline in the hard carbon matrix; in the VC mixer; rotating speed mixing 30min with 1600r/min; then put into chamber type electric resistance furnace; with the heating rate to 1000 ℃ of 2 ℃/min, insulation 8h, processed; under nitrogen protection, carry out, nitrogen flow is 0.8m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 10
(1) solidify: add 55g curing agent polyamide in the mixture of 15g epoxy resin and 30g furfural phenol resin, adopt high speed dispersor, rotating speed is 2200r/min, and the time is 120min, solidify 35h in air, under 80 ℃, obtain the precuring presoma.
(2) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 1100 ℃ of 4 ℃/min, pyrolysis 4h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.8m
3/ h.
(3) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 18 μ m, obtains the hard carbon matrix.
(4) coat: add 18g coating presoma poly m-phenylene diamine in the hard carbon matrix; in the VC mixer; rotating speed mixing 50min with 2500r/min; then put into chamber type electric resistance furnace; with the heating rate to 1300 ℃ of 2 ℃/min, insulation 1h, processed; under nitrogen protection, carry out, nitrogen flow is 0.3m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 11
(1) solidify: add 40g alloy organic siliconresin in the mixture of 20g phenolic resins and 40g epoxy resin, adopt high speed dispersor, rotating speed is 1500r/min, and the time is 80min, in air, under 150 ℃, solidifies 10h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 20 μ m.
(3) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 750 ℃ of 9 ℃/min, pyrolysis 3h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.5m
3/ h.
(4) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 14 μ m, obtains the hard carbon matrix.
(5) coat: add 20g coating presoma polyacrylonitrile in the hard carbon matrix; in the VC mixer; rotating speed mixing 60min with 1500r/min; then put into chamber type electric resistance furnace; with the heating rate to 1000 ℃ of 4 ℃/min, insulation 4h, processed; under nitrogen protection, carry out, nitrogen flow is 0.7m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 12
(1) solidify: add 50g curing agent melamine resin in the 50g furfural phenol resin, adopt high speed dispersor, rotating speed is 3000r/min, and the time is 70min, in air, under 100 ℃, solidifies 20h, obtains the precuring presoma.
(2) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 950 ℃ of 14 ℃/min, pyrolysis 2h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.5m
3/ h.
(3) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 20 μ m, obtains the hard carbon matrix.
(4) coat: add 3g coating presoma pitch in the hard carbon matrix; in the VC mixer; rotating speed mixing 55min with 1700r/min; then put into chamber type electric resistance furnace; with the heating rate to 1000 ℃ of 6 ℃/min, insulation 2h, processed; under nitrogen protection, carry out, nitrogen flow is 0.5m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 13
(1) solidify: add 1g adulterant oxidation cobalt in the mixture of 1g phenolic resins and 9g Merlon, 89g curing agent benzene sulfonic acid, adopt high speed dispersor, rotating speed is 5000r/min, time is 15min, solidifies 12h in air, under 70 ℃, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 50 μ m.
(3) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 1350 ℃ of 20 ℃/min, pyrolysis 0.5h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 1.2m
3/ h.
(4) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 2 μ m, obtains the hard carbon matrix.
(5) coat: add 50g coating presoma Kynoar in the hard carbon matrix; in the VC mixer; rotating speed mixing 150min with 1200r/min; then put into chamber type electric resistance furnace; with the heating rate to 1550 ℃ of 20 ℃/min, insulation 0.3h, processed; under nitrogen protection, carry out, nitrogen flow is 1.2m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Embodiment 14
(1) solidify: in air, solidify 0.5h under 300 ℃, with 20g alloy sodium phosphate, at rotating speed, be then to stir 15min under 3500r/min to mix by the mixture of 16g polybutadiene and 64g polyvinyl chloride, obtain the precuring presoma.
(2) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 500 ℃ of 15 ℃/min, pyrolysis 60h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.1m
3/ h.
(3) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 2 μ m, obtains the hard carbon matrix.
(4) coat: add 0.8g coating presoma polyphenylene sulfide in the hard carbon matrix; in the VC mixer; rotating speed mixing 15min with 4000r/min; then put into chamber type electric resistance furnace; with the heating rate to 700 ℃ of 16 ℃/min, insulation 30h, processed; under nitrogen protection, carry out, nitrogen flow is 0.2m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains low-cost lithium ion power and energy-storage battery hard carbon cathode material.
Comparative Examples 1 and Comparative Examples 2 adopt prior art to prepare the lithium ion hard carbon cathode material.
Comparative Examples 1
(1) pyrolysis: the 100g acrylic resin is put into to chamber type electric resistance furnace, with the heating rate of 18 ℃/min, be warming up to 1050 ℃, pyrolysis 2h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.8m
3/ h.
(2) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 18 μ m, obtains the hard carbon matrix.
(3) coat: add 10g coating presoma aniline in the hard carbon matrix; in the VC mixer; rotating speed mixing 50min with 1400r/min; then put into chamber type electric resistance furnace; with the heating rate to 1100 ℃ of 18 ℃/min, insulation 2h, processed; under nitrogen protection, carry out, nitrogen flow is 0.6m
3/ h naturally is cooled to room temperature in box type furnace, crosses 200 mesh sieves, obtains the lithium ion hard carbon cathode material.
Comparative Examples 2
(1) precuring: add 10g alloy organic siliconresin in the 75g furfuryl alcohol resin, adopt high speed dispersor, rotating speed is 1200r/min, and the time is 80min, in air, under 220 ℃, solidifies 8h, obtains the precuring presoma.
(2) fragmentation: adopt planetary ball mill that the precuring presoma is carried out to ball milling, obtain the powder particle that particle mean size is 24 μ m.
(3) solidify: add the curing agent aniline of 15g in powder, stir, solidify 20h under 90 ℃, obtain solid precursor.
(4) pyrolysis: will solidify presoma and put into chamber type electric resistance furnace, with the heating rate to 500 ℃ of 15 ℃/min, pyrolysis 60h, be cooled to room temperature naturally, makes hard carbon, and pyrolysis is carried out under nitrogen atmosphere, and nitrogen flow is 0.1m
3/ h.
(5) fragmentation: adopting planetary ball mill that hard carbon is milled to particle mean size is 8 μ m, crosses 200 mesh sieves, obtains the lithium ion hard carbon cathode material.
Low-cost lithium ion power and the energy-storage battery hard carbon cathode material of embodiment 1 ~ 14 preparation, adopt the KYKY2800B flying-spot microscope observation pattern of Beijing KYKY Technology Development Co., Ltd., be shaped as irregular bulk, fine particle, the NOVA1000 specific-surface area detection instrument test that adopts U.S. QUANTA CHROME company is loose structure, pore-size distribution is 0.5～80nm, and porosity is 10～17%.Adopt PW3040/60X ' the Pert x-ray diffractometer test crystal layer spacing d of Dutch PANalytical instrument company
002between 0.341～0.472nm, adopting the Mastersizer2000 type laser particle size analyzer test particle size range of Britain Ma Erwen Instrument Ltd. is 0.8～82 μ m, and adopting the full-automatic specific area of Tristar3000 of Micromeritics Instrument Corp. U.S.A and lacunarity analysis instrument test specific area is 1.92～72.0m
2/ g, adopting the full-automatic real density analyzer test of the Ultrapycnometer1000 type real density of U.S. Kang Ta instrument company is 1.58～2.32g/cm
3, the FZS4-4 type tap density instrument of the employing long-range Science and Technology Ltd. in Chinese and Western, Beijing, the test tap density is 0.89～1.42g/cm
3.
The method of testing of carbon residue amount: 1, in clean crucible, put into sample, dry 1h in 110 ℃ ± 5 ℃ baking ovens; 2, clean porcelain Noah's ark is placed in the Muffle furnace of 950 ℃ ± 50 ℃ and calcines 1h, cooling 2min in air, then put into the porcelain Noah's ark the cooling 30min of drier, is chilled to room temperature, and weighing, be accurate to 0.0001g; 3, repeating step 2, until the difference of consecutive weighings is no more than 0.0004g, the quality of porcelain Noah's ark are designated as to m
1; 4, weighing is about the dried sample of 1g to the porcelain Noah's ark, is accurate to 0.0001g, is designated as m
2; The porcelain Noah's ark that 5, will fill sample is put in the Muffle furnace of 950 ℃ ± 50 ℃ and is calcined 1.5h, then take out the porcelain Noah's ark in air after cooling 2min, put into the cooling 30min of drier, be cooled to weighing after room temperature, be accurate to 0.0001g, repeating step 5, until the difference between consecutive weighings is no more than 0.0004g, is designated as m
3.
Be calculated as follows the content of C element: C%=[((m
2-m
3)/(m
2-m
1)] * 100%, in formula: m
1for porcelain Noah's ark quality, m
2for the quality of porcelain Noah's ark and sample, m
3quality for porcelain Noah's ark and ash content.Low-cost lithium ion power prepared by method of the present invention and energy-storage battery hard carbon cathode material, the content of C element is higher than 90.6%.
To contrast row 1～2 sample and test as stated above sign, test result refers to table 3.
Negative material prepared by embodiment, with binding agent polyvinylidene fluoride PVDF, conductive agent Super-P, according to the mass ratio of 92:5:3, mix, add 1-METHYLPYRROLIDONE NMP as dispersant furnishing slurry, evenly be coated on 10 μ m thickness Copper Foils, compacting in flakes, is then made the circular carbon membrane of diameter 1cm, and in drying box, under 110 ℃, oven dry 12h is standby, using metal lithium sheet as to the utmost point, use 1mol/L LiPF
6three component mixed solvents press the electrolyte that the volume ratio of EC:DMC:EMC=1:1:1 mixes, microporous polypropylene membrane is barrier film, be assembled into simulated battery (the German Braun inert atmosphere glove box MB200B of System Co., Ltd type) in being full of the glove box of argon gas, the charge-discharge test of simulated battery is on the new prestige battery detection equipment BTS-5V100mA of the Co., Ltd battery testing system of Shenzhen, charging/discharging voltage is limited in 0.001～2.0 volt, 40C, 30C, 1C, 0.2C, test reversible capacity and enclosed pasture efficiency first first, an enclosed pasture efficiency calculation formula is first: the discharge capacity of enclosed pasture efficiency=initial charge capacity/first first.
To contrast row 1～2 as negative material, and prepare as stated above battery, and then carry out electrochemical property test, its test result refers to table 4.
As shown in Figure 1, the shape that the material of embodiment 1 preparation is irregular bulk, size is relatively even, has microcellular structure.
As shown in Figure 2, the d of the material of embodiment 1 preparation
002=0.383, its micropore, irregular structure make it than general graphite type material d
002it is large that interlamellar spacing is wanted.
As shown in Figure 3, I
d/ I
g=0.842, its micropore, irregular structure make it larger than general graphite type material.
As shown in Figure 4, at normal temperatures, under 40C, 30C high magnification condition, 40C/1C charging capacity conservation rate is that 93.4%, 30C/1C charging capacity conservation rate is 95.4%, and its micropore, irregular structure make its high-rate charge-discharge capability excellence.
From experimental result, hard carbon cathode material capacity prepared by the method for the invention is high, and enclosed pasture efficiency is high first, and the high rate performance excellence, be desirable lithium ion battery negative material.
The formula of embodiment 1 ~ 14 and Comparative Examples 1～2 is in Table 1, and process conditions are in Table 2, and structured testing is in Table 3, and electric performance test the results are shown in Table 4.
Table 1
Annotate: percentage described in table 1 is all the percentage that accounts for hard carbon matrix precursor gross mass.
Table 2
Table 3
Table 4
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. the preparation method of a hard carbon cathode material, is characterized in that, described method comprises: the thermal decomposition product of mixture of thermosetting resin or thermosetting resin and thermoplastic resin of take is the hard carbon matrix, and adopting material with carbon element is that coating obtains hard carbon cathode material.
2. the method for claim 1, is characterized in that, said method comprising the steps of:
(1) the hard carbon matrix precursor is solidified, obtain solid precursor, wherein, described hard carbon matrix precursor contains resin, the mixture that described resin is thermosetting resin or thermosetting resin and thermoplastic resin, and thermoplastic resin is 0～90% of resin gross mass;
(2) solid precursor step (1) obtained carries out pyrolysis, obtains the hard carbon matrix;
(3) hard carbon matrix step (2) obtained mixes with the coating presoma, and pyrolysis, obtain hard carbon cathode material, and the mass ratio of wherein said coating presoma and hard carbon matrix precursor is 0.8:100 ~ 50:100.
3. method as claimed in claim 1 or 2, it is characterized in that, step (1) comprising: precuring after resin is mixed with alloy, broken, with curing agent, mix, obtain the hard carbon matrix precursor, then solidify, obtain solid precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, and thermoplastic resin is 0～90% of resin gross mass, described alloy is 0 ~ 20% of described hard carbon matrix precursor gross mass, and described curing agent is 0 ~ 90% of described hard carbon matrix precursor gross mass;
Preferably, step (1) comprising: resin is mixed with alloy and/or curing agent, obtain the hard carbon matrix precursor, then solidify, obtain solid precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, thermoplastic resin is 0～90% of resin gross mass, and described alloy is 0 ~ 20% of described hard carbon matrix precursor gross mass, and described curing agent is 0 ~ 90% of described hard carbon matrix precursor gross mass;
Preferably, step (1) comprising: by resin solidification, obtain solid precursor, then with alloy, mix, obtain the hard carbon matrix precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, thermoplastic resin is 0～90% of resin gross mass, and described alloy is 0 ~ 20% of described hard carbon matrix precursor gross mass.
4. as the described method of claim 1-3 any one, it is characterized in that, described thermosetting resin is a kind or the combination of at least 2 kinds in furfural phenol resin, furfuryl alcohol resin, polybutadiene, melamine resin, epoxy resin, phenolic resins, polyurethane and Lauxite;
Preferably, described thermoplastic resin is a kind or the combination of at least 2 kinds in acrylic resin, Merlon, polyvinyl chloride, polyurethane and polyformaldehyde;
Preferably, described coating presoma is a kind or the combination of at least 2 kinds in ethyl-methyl carbonic ester, butadiene-styrene rubber, citric acid, epoxy resin, phenolic resins, pitch, poly(ethylene oxide), PPOX, polyimides, polypyrrole, polyaniline, polyethylene glycol imines, poly m-phenylene diamine, polythiophene, polyacrylonitrile, polytetrafluoroethylene, Kynoar, polyphenylene sulfide, polymethyl methacrylate and poly-phenylene vinylene (ppv).
5. as the described method of claim 2-4 any one, it is characterized in that, described alloy is a kind or the combination of at least 2 kinds in metal simple-substance, non-metal simple-substance, metallic compound and nonmetallic compound;
Preferably, described metal simple-substance is a kind or the combination of at least 2 kinds in copper, iron, nickel, cobalt, manganese, titanium, vanadium, chromium, tin and antimony;
Preferably, described metallic compound is metal oxide, metal hydroxides, metal phosphate, the metal tripolyphosphate hydrogen salt, 1 kind or the combination of at least 2 kinds in metal halide and metal acetate, nickel oxide more preferably, cobalt oxide, tin ash, manganese dioxide, titanium dioxide, vanadic oxide, mangano-manganic oxide, di-iron trioxide, chrome green, Kocide SD, nickel hydroxide, cobalt hydroxide, sodium phosphate, sodium dihydrogen phosphate, 1 kind or the combination of at least 2 kinds in stannic chloride and tin acetate, be particularly preferably nickel oxide, cobalt oxide, Kocide SD, nickel hydroxide, cobalt hydroxide, sodium phosphate, sodium dihydrogen phosphate, 1 kind or the combination of at least 2 kinds in stannic chloride and tin acetate,
Preferably, described non-metal simple-substance is a kind or the combination of at least 2 kinds in boron, phosphorus, silicon and sulphur, is particularly preferably a kind or the combination of at least 2 kinds in boron, silicon and sulphur;
Preferably, described nonmetallic compound is a kind or the combination of at least 2 kinds in borate, boric acid, borate, silicic acid, silicate, esters of silicon acis, Si oxide, phosphate, phosphate, phosphoric acid, phosphorous oxides, sulfuric acid and sulfate, is particularly preferably a kind or the combination of at least 2 kinds in boric acid, glycol borate, silicon boride, boron chloride, silicon dioxide, silicic acid, organic siliconresin, ammonium sulfate, phosphorus pentoxide, phosphoric acid, ammonium phosphate, phosphoric acid dihydro amine;
Preferably, described curing agent is a kind or the combination of at least 2 kinds in m-phenylene diamine (MPD), aniline, hexamethylene diamine, melamine, melamine resin, benzene sulfonic acid, hexamethylenetetramine, polyamide and phthalic anhydride.
6. as the described method of claim 1-5 any one, it is characterized in that, described thermoplastic resin is 0～88% of resin gross mass, is particularly preferably 0 ~ 85%;
Preferably, described alloy is 0 ~ 18% of described hard carbon matrix precursor gross mass, is particularly preferably 0 ~ 15%;
Preferably, described curing agent is 0 ~ 88% of described hard carbon matrix precursor gross mass, is particularly preferably 0 ~ 85%;
Preferably, described being solidificated in air of step (1) carried out;
Preferably, the described curing temperature of step (1) is 70 ~ 300 ℃, more preferably 75 ~ 280 ℃, is particularly preferably 80 ~ 250 ℃;
Preferably, step (1) described curing time is at least 0.5 hour, more preferably 0.8 ~ 80 hour, more preferably 1 ~ 60 hour, is particularly preferably 1 ~ 24 hour;
Preferably, the described precuring of step (1) is carried out in air;
Preferably, the described precuring temperature of step (1) is 70 ~ 300 ℃, more preferably 75 ~ 280 ℃, is particularly preferably 80 ~ 250 ℃;
Preferably, the described precuring time of step (1) is at least 0.5 hour, more preferably 0.8 ~ 60 hour, is particularly preferably 1 ~ 40 hour;
Preferably, the product of the described precuring of step (1) is carried out to fragmentation; Preferably, described mechanical crushing or the ball milling of being broken for; Preferably, described broken terminal is particle diameter 2～50 μ m.
7. as the described method of claim 2-6 any one, it is characterized in that, the described pyrolysis temperature of step (2) is 500 ~ 1350 ℃, more preferably 550 ~ 1300 ℃, is particularly preferably 580 ~ 1200 ℃;
Preferably, reach heating rate before the described pyrolysis temperature of step (2) and be 20 ℃/below min, more preferably 15 ℃/below min, be particularly preferably 0.5 ~ 8 ℃/min;
Preferably, the described pyrolysis time of step (2) is at least 0.3 hour, more preferably 0.5 ~ 10 hour, is particularly preferably 0.6 ~ 7.2 hour;
Preferably, the described pyrolysis of step (2) is carried out under inert gas shielding; Preferably, described inert gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton and xenon, is particularly preferably nitrogen; Preferably, described inert gas flow is 0.1～1.2m
3/ h, more preferably 0.14～1m
3/ h, be particularly preferably 0.18～0.88m
3/ h;
Preferably, naturally be cooled to room temperature after the described pyrolysis of step (2);
Preferably, hard carbon matrix step (2) obtained carries out fragmentation; Preferably, described mechanical crushing or the ball milling of being broken for; Preferably, described broken terminal is particle diameter 2～50 μ m;
Preferably, the mass ratio of described coating presoma and hard carbon matrix precursor is 1:100 ~ 45:100, is particularly preferably 1.2:100 ~ 40:100.
8. as the described method of claim 2-7 any one, it is characterized in that, step (3) is described is mixed into stirring; Preferably, described mixing speed is 1200～4000r/min, and more preferably 1400～3500r/min, be particularly preferably 1500～3300r/min;
Preferably, the described incorporation time of step (3) is at least 15 minutes, more preferably 20 ~ 55 minutes, is particularly preferably 28 ~ 48 minutes;
Preferably, the described pyrolysis temperature of step (3) is 700 ~ 1550 ℃, more preferably 750 ~ 1500 ℃, is particularly preferably 800 ~ 1400 ℃;
Preferably, reach heating rate before the described pyrolysis temperature of step (3) and be 20 ℃/below min, more preferably 12 ℃/below min, be particularly preferably 1.2 ~ 7.2 ℃/min;
Preferably, the described pyrolysis time of step (3) is at least 0.3 hour, more preferably 1 ~ 10 hour, is particularly preferably 2 ~ 8 hours;
Preferably, naturally be cooled to room temperature after the described pyrolysis of step (3);
Preferably, the described pyrolysis of step (3) is carried out under inert gas shielding; Preferably, described inert gas is a kind or the combination of at least 2 kinds in nitrogen, helium, neon, argon gas, Krypton and xenon, is particularly preferably nitrogen; Preferably, described inert gas flow is 0.1～1.2m
3/ h, more preferably 0.14～1m
3/ h, be particularly preferably 0.18～0.88m
3/ h.
9. method as described as claim 1-8, is characterized in that, said method comprising the steps of:
(1) by mass percentage by 80 ~ 100% resin and 0 ~ 20% alloy, at rotating speed, be under 1500～5000r/min, stir at least 15min to evenly, solidify at least 0.5h in air, under 70 ~ 300 ℃, obtain solid-state precursor, wherein, described resin comprises the mixture of thermosetting resin or thermosetting resin and thermoplastic resin, and thermoplastic resin is 0～90% of resin gross mass;
(2) the following heating rate to 500 ~ 1350 ℃ with 20 ℃/min, pyrolysis is 0.3h at least, naturally is cooled to room temperature, then carries out fragmentation, and obtaining granularity is the hard carbon matrix of 2～50 μ m;
(3) add the coating presoma in the hard carbon matrix, rotating speed with 1200～4000r/min mixes at least 15min, then the following heating rate to 700 ~ 1550 ℃ with 20 ℃/min, time is 0.3h at least, carry out the coating pyrolysis processing, naturally be cooled to room temperature, obtain the lithium ion battery hard carbon cathode material, the mass ratio of wherein said coating presoma and hard carbon matrix precursor is 0.8:100 ~ 50:100.
10. the hard carbon cathode material prepared by the described method of claim 1-9 any one, it is irregular block fine particle, particle size range is 0.8～82 μ m, there is pore structure, aperture is 0.5～80nm, and porosity is 10～17%, and specific area is 1.92～72.0m
2/ g, crystal layer spacing d
002be 0.341～0.472nm, real density is 1.58～2.32g/cm
3, tap density is 0.89～1.42g/cm
3, the content of its C element is higher than 90.6%.
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Address after: 158100 leap forward Committee of Mashan District Central Community, Jixi City, Heilongjiang Province Patentee after: Jixi beiteri New Energy Technology Co.,Ltd. Patentee after: Jixi Super Carbon Technology Co.,Ltd. Patentee after: Beitrei New Materials Group Co.,Ltd. Address before: 158100 leap forward Committee of Mashan District Central Community, Jixi City, Heilongjiang Province Patentee before: JIXI BTR GRAPHITE INDUSTRIAL PARK Co.,Ltd. Patentee before: Jixi Super Carbon Technology Co.,Ltd. Patentee before: Beitrei New Materials Group Co.,Ltd. |
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| CP01 | Change in the name or title of a patent holder |