CN106006603A - Preparation method of hard carbon microsphere anode material for lithium ion batteries - Google Patents
Preparation method of hard carbon microsphere anode material for lithium ion batteries Download PDFInfo
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- CN106006603A CN106006603A CN201610337472.5A CN201610337472A CN106006603A CN 106006603 A CN106006603 A CN 106006603A CN 201610337472 A CN201610337472 A CN 201610337472A CN 106006603 A CN106006603 A CN 106006603A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010405 anode material Substances 0.000 title abstract description 6
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- 239000007789 gas Substances 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229920001592 potato starch Polymers 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
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- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
- 230000002427 irreversible effect Effects 0.000 description 7
- 229910052754 neon Inorganic materials 0.000 description 7
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 7
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- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of hard carbon microsphere anode material for lithium ion batteries and belongs to the technical field of lithium ion battery anode materials. Natural starch is used as a raw material and is subjected to thermal stabilization and high-temperature carbonization to prepare the starch-based hard carbon microsphere anode material, a fluidized bed reactor is used in the preparation process as a stabilizing or carbonizing device for the starch, and the natural starch is thermally stabilized or carbonized in a fluidic form. The method enables increased stabilization temperature, shortened stabilization time and improved preparation efficiency; the method may solve the mass transfer and heat transfer problems in the stabilization process and facilitate large-scale production; meanwhile, the hard carbon microsphere anode material for lithium ion batteries prepared by the method has better electrochemical properties.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, be specifically related to the preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery.
Background technology
Lithium ion battery because having that energy density is high, power characteristic is good, running voltage is high, have extended cycle life, the advantage such as pollution-free, make it be with a wide range of applications in many-sides such as portable electric appts, electric automobile, space technology, national defense industry, become the study hotspot the most widely paid close attention to.
Carbon Materials is the preferable negative material of lithium ion battery, and wherein graphite type material is current most widely used carbon cathode material.In the last few years, advancing by leaps and bounds using lithium ion battery as the development of the portable electric appts of power supply, lithium ion battery is also gradually being pushed to traffic dynamic field simultaneously, so the requirement to lithium ion battery is also constantly improving.Along with this higher requirement, graphite cathode material is the most obvious in the limitation of the aspects such as specific energy, power characteristic, cycle characteristics and safety.
Hard carbon material has higher specific capacity, superior fast charging and discharging ability, the chemical property that good cyclical stability and higher safety etc. are excellent, is to be hopeful very much one of negative material substituting conventional graphite class material.The hard carbon cathode material pattern that different initiation materials and preparation method prepare is different, wherein the hard carbon cathode material of ball-type pattern is because having higher bulk density, low surface-to-volume ratio and higher mechanical performance, thus the lifting of beneficially hard carbon material chemical property, it is hot research direction.
At present, it is expensive generally to there are the prices of raw materials in the hard carbon microsphere cathode material of lithium ion battery, non-renewable, the problems such as environment is unfriendly.Additionally, the most complex process of preparation method of hard carbon microspheres, working condition is harsh, is not suitable for scale of mass production.Thus, the problems referred to above significantly limit the commercialization process of the hard carbon microsphere cathode material of lithium ion battery.
With starch as initiation material, process through special process, the carbon microspheres material of the quasi ball-type pattern keeping starch granules can be prepared.This is a kind of novel carbon microspheres preparation method, has an advantage in that: first, starch material wide material sources, renewable and environmental friendliness；Additionally, because avoiding the balling-up operation generally existed in carbon microspheres preparation process so that the technical process that this method prepares carbon microspheres is the simplest.
Document " Spherical hard carbon prepared from potato starch using
as anode material for Li-ion batteries”
In (Materials Letters 65 (2011) 3368-3370), hard for starch base carbon microspheres material is used as ion secondary battery cathode material lithium by author first, obtains the hard carbon microsphere cathode material of lithium ion battery with good electric chemical property.
Li Wenbins etc. are in Publication No. CN103647082A, publication date is on March 19th, 2014, the patent of invention of entitled " preparation method of a kind of lithium ion secondary battery hard-carbon microsphere negative electrode " discloses one at reduced pressure conditions, the method preparing the hard carbon microsphere cathode material of lithium ion battery by stabilisation and carbonization process, the method can suppress the caking tendency of carbonization afterproduct, reduce the irreversible capacity of hard carbon microsphere cathode material, also have certain help for promoting the cyclical stability of material.In said method, in order to avoid starch granules foaming in carbonization process and agglomeration problems, needing to take to carry out starch at a lower temperature the mode of long-time heating stabilizing treatment, the preparation time causing hard carbon microspheres is long.
Kings etc. are in Publication No. CN102683661A, publication date is JIUYUE in 2012 19, in the patent of invention of entitled " preparation method of the hard carbon cathode material of a kind of lithium ion battery ", disclose a kind of with starch as raw material, through catalyst solution dipping, dry, zone heating, repeatedly pickling and drying and other steps, the method being prepared for the hard carbon microsphere cathode material of lithium ion battery.In this invention, due to the effect of catalyst, shorten the heat treatment time in hard carbon microspheres preparation process to a certain extent.But, owing to wet starch can occur gelatinizings at 50 80 DEG C, therefore in this method, dry run after catalyst solution impregnation steps needs the most slowly to carry out, and adds the preparation time of carbon microspheres.Additionally, the repeatedly pickling after high temperature carbonization and drying steps, also can increase the preparation time of carbon microspheres, the most also can introduce active function groups on carbon microspheres surface, increase the irreversible capacity of material and affect the cyclical stability of material.Thus, the method is difficult to be obviously improved the preparation efficiency of the hard carbon microspheres of starch base, and whole preparation process also can be made to become relatively complicated, runs counter to the starch base hard carbon microspheres simple original intention of preparing technique process.
The problem of starch base hard carbon microspheres manufacturing cycle length, is largely determined by stabilization procedures.With accumulation mode, material is heated, because starch granules transfixion, so higher stabilization temperature can cause melting also between the starch granules contacted with each other for a long time, cause caking phenomenon, thus scattered starch base hard carbon microspheres material cannot be prepared.In order to prevent the generation of above-mentioned situation, it is necessary to take relatively low stabilization temperature that starch granules raw material is carried out stabilizing treatment.Relatively low stabilization temperature, has delayed stabilisation process, it is therefore desirable to the longer time can be only achieved required stabilization effect, with ensure in the high-temperature heating process in later stage starch granules there is not foaming and melt and etc. phenomenon.Although, Above-mentioned catalytic method can reduce stabilization temperature and accelerate stabilisation process, but too increases the complexity of carbon microspheres preparation technology simultaneously, and constrains the performance of starch base hard carbon microsphere cathode material electrical property to a certain extent.
Additionally, carry out above-mentioned preparation method needing bigger inventory when technique is amplified, in said method, the mode of heating of taked stacked can bring serious heat transfer and mass transfer problem, the performance of anticathode material to be negatively affected when the time comes.The stockpile amplified, first, can hinder heat conduction in starch material heap in heating process, causes the inhomogeneities of temperature in stockpile, and the stabilization temperature being both not easy to raw starch controls, and can affect again the concordance of product；Additionally, the diffusion generating light component materials also can be hindered, increase light side reaction between component materials and carbon microspheres in heating process, cause the increase of material irreversible capacity and affect the cycle performance of material.
Summing up, present in current starch base hard carbon microsphere cathode material preparation method, technical problem underlying includes: first, and preparation flow complexity, manufacturing cycle length, preparation efficiency are low；Second, the technique that heat transfer, mass transfer problem cause amplifies difficulty；3rd, the chemical property of material can be had a negative impact by some step in preparation process.
Summary of the invention
For problems of the prior art, a kind of method that it is an object of the invention to provide hard carbon microsphere cathode material of lithium ion battery starch base keeping native starch particles primary morphology with native starch for raw material preparation.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery, comprises the steps
1) native starch raw material is put in fluidized-bed reactor, being continually fed into carrier gas makes native starch raw material be fluidized state, gradually promoting the temperature in fluidized-bed reactor, the heat stabilization that native starch raw material carries out in 180 280 DEG C of temperature ranges fluidized state processes；
2) under inert gas shielding, the starch after stabilizing treatment in step 1) is carried out the high temperature carbonization process of 700 1800 DEG C, after cooling, obtains the hard carbon microsphere cathode material of lithium rechargeable battery starch base.
As preferably, in described step 1), the heat stabilization process time is 1 36h.
As preferably, described native starch is at least one in native potato starch, native corn starch, Native tapioca starch, natural sweet potato starch, native wheat starch, native rice starch or native pea starch.
As preferably, the carrier gas in described step 1) is at least one in dry air, oxygen, nitrogen or argon.
As preferably, the gas speed in fluidized-bed reactor of the carrier gas in described step 1) is 0.01 6.9cm/s.
As preferably, the lifting of the fluidized-bed reactor temperature in described step 1) is to realize by the way of heating flows to fluidized-bed reactor carrier gas.
As preferably, when in described step 1), heat stabilization processes, in fluidized-bed reactor, temperature gradually rises.
As preferably, the temperature in described fluidized-bed reactor raises with stabilizing treatment linearly.
As preferably, when in described step 1), starch is in fluidized state, carry out separating and sending back in fluidized-bed reactor by the starch granules of carrier gas entrained with, to improve stabilization step yield by being arranged on the solid and gas segregation apparatus of fluidized-bed reactor rear end.
As preferably, described solid and gas segregation apparatus is cyclone separator.
Further technical scheme is: described step 2) in high temperature carbonization process step, it is after stabilizing treatment step 1) completes, using noble gas as carrier gas, the starch after stabilisation is made in fluidized-bed reactor to keep fluidized state, and promote the temperature in fluidized-bed reactor to 280 450 DEG C, starch after stabilisation in step (1) carries out the pre-carbonization under fluidized state process, again pre-carbonization process material is put in high temperature carbonization furnace after cooling, under inert atmosphere, carry out the high temperature carbonization process of 700 1800 DEG C.
May be used without following technical scheme: described step 2) it is after stabilizing treatment step 1) completes, using noble gas as carrier gas, the starch after stabilisation is made in fluidized-bed reactor to keep fluidized state, and promote the temperature in fluidized-bed reactor to 700 1800 DEG C, stabilisation starch is carried out the high temperature carbonization under fluidized state and processes.
Described step 2) in 700 1800 DEG C high temperature carbonization process the time be 10min 10h.
Described step 2) in noble gas be at least one in nitrogen or argon.
The invention has the beneficial effects as follows:
The present invention carries out stabilizing treatment at fluidized state to native starch, is separated from each other between starch granules, compares the heat stabilization process of stacking states, even if improving stabilizing treatment temperature melting and and caking phenomenon between starch granules also will not occur.Thus, stabilizing treatment can be carried out at a higher temperature, it is possible to accelerate stabilisation process, be greatly shortened the stabilizing treatment time, promote preparation efficiency.
The present invention carries out stabilisation or carbonization processes at fluidized state to native starch, compares heat stabilization or the high temperature carbonization process of stacking states, can avoid or alleviate occur because contacting with each other between starch granules melt also, caking phenomenon.
The present invention carries out stabilisation or carbonization processes at fluidized state to native starch, reactor temperature is uniform, the homogeneity of product offset issue caused because temperature is uneven when avoiding heat stabilization or the carbonization of stacking states, can promote the concordance of the hard carbon microsphere cathode material of prepared starch base.
The present invention uses fluidized-bed reactor that native starch particles carries out stabilisation or carbonization processes and prepares hard carbon microspheres, on the one hand, heat transfer when can solve to prepare on a large scale hard carbon microsphere cathode material and mass transfer problem, on the other hand, the correlation technique of fluidized-bed reactor is the most ripe, thus the method is easier to make for industry amplification, it is suitable for extensive preparation.
The present invention carries out stabilisation or carbonization processes at fluidized state to native starch, mass transfer velocity is fast, the generation of the bad side reaction that the Long contact time of the light-component gas and starch particle surface that avoid effusion causes, reduce product surface functional group content, efficiency first or the cycle characteristics of the hard carbon microsphere cathode material of prepared starch base can be promoted.
Accompanying drawing explanation
Fig. 1 is fluidized bed reaction schematic diagram used by patent of the present invention；
Fig. 2 is the electron scanning micrograph of the hard carbon microsphere cathode material of potato starch base using the inventive method to prepare.
Each reference is: 1 fluidized-bed reactor, 2 temperature controllers, 3 outer wall heaters, 4 raw materials mouths, 5 air distribution plates, 6 carrier gas heater, 7 temperature sensors, 8 solid-gas separators.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in further detail.
Fig. 1 is the structural representation of fluidized bed reaction used in the present invention, this figure is only the schematic diagram of fluidized bed reaction, in order to embodiments of the present invention to be described, can not represent actually used fluidized bed reaction completely, actually used fluidized bed reaction is also not necessarily limited to preparation facilities shown in schematic diagram.
nullThis preparation facilities includes fluidized-bed reactor 1 and the outer wall heater 3 being coated on fluidized-bed reactor 1，Described fluidized-bed reactor 1 upper and lower side is connected to exhaustor and air inlet pipe，Carrier gas heater 6 it is provided with in described air inlet pipe，The described left and right sides, fluidized-bed reactor 1 lower end is connected to charge pipe and drainage conduit，Raw materials mouth 4 it is provided with on described charge pipe，It is provided with discharging opening in described drainage conduit，Connect between described drainage conduit and exhaustor and have solid-gas separator 8，It is provided with temperature sensor 7 in described fluidized-bed reactor 1，Connect in described temperature sensor 7 and have temperature controller 2，Described outer wall heater 3 and carrier gas heater 6 are connected with temperature controller 2，The air distribution plate 5 being positioned at below charge pipe and drainage conduit it is additionally provided with in described fluidized-bed reactor 1.
The temperature that preparation facilities of the present invention is jointly monitored by temperature sensor 7, temperature controller 2, outer wall heater 3 and carrier gas heater 6, controlled in fluidized-bed reactor: temperature sensor 7 sends the temperature signal within fluidized-bed reactor 1 to temperature controller 2, temperature controller 2 is according to the temperature signal monitored, outer wall heater 3 or carrier gas heater 6 send thermal control signals, thus realize the regulation of temperature in reactor 1.
In lithium rechargeable battery hard carbon microspheres preparation process, first by raw starch, (raw starch is native starch, it is not particularly limited Starches, as natural grain kind of starch can be used, tubers starch, bean starch or fruit kind of starch etc., with native potato starch, corn starch, tapioca, sweet potato starch, wheaten starch, rice starch or pea starch are as preferably) join (stabilisation that fluidized-bed reactor 1 is carried out under fluidized state by starch fluidized-bed reactor 1 from charge door 4, the reaction vessel that pre-carbonization or high temperature carbonization process)；(carrier gas can be any gas nontoxic, harmless, free from environmental pollution to be passed through carrier gas, it is preferably one or more in dry air, oxygen, nitrogen or argon), carrier gas enters reactor after carrier gas heater 6 bottom fluidized-bed reactor, after air distribution plate 5 is uniformly distributed, raw starch is kicked up, making it is fluidized state, during i.e. starch granules is suspended in the carrier gas of motion, is mutually disengaged contact and without phase mutual friction between starch granules.
When starch is in fluidized state, part material can be by carrier gas picks, and the raw material that carrier gas gas speed is carried secretly the most greatly is the most.Therefore, at least one embodiment of the invention, gas-solid separating device 8 as shown in the figure are set at fluidized-bed reactor 1 end, send back to after the starch granules carried secretly is separated from outlet carrier gas in fluidized-bed reactor 1 and continue to participate in reaction.In at least one embodiment of the invention, gas-solid separating device 8 uses cyclone separator.It addition, at least one embodiment of the invention, gas-solid separating device 8 is the other kinds of gas-solid separating device beyond cyclone separator, such as dedusting airbag etc..
As described in art solutions of the present invention, in lithium ion secondary battery hard-carbon microsphere negative electrode preparation process, can carry out the stabilizing treatment of 180 280 DEG C in a fluidized bed reactor, the pre-carbonization of 280 450 DEG C processes or the high temperature carbonization of 700 1800 DEG C processes.During stabilizing treatment, preferably carrier gas heater 6 heats that (mode at least one embodiment of the invention, using carrier gas heater heating carrier gas promotes temperature in fluidized-bed reactor to flowing through carrier gas；Other mode of heatings can be used equally to promote reactor temperature, as used the mode of outer wall heating devices heat at least one embodiment of the invention to promote temperature in fluidized-bed reactor), in making fluidized-bed reactor 1, temperature gradually rises, thus meets stabilization temperature requirement.If carry out pre-carbonization or high temperature carbonization process in fluidized-bed reactor 1, temperature in fluidized-bed reactor 1 possibly cannot be promoted to target temperature by simple use carrier gas heater 6, then can jointly promote temperature in fluidized-bed reactor 1 by outer wall heater 3 and carrier gas heater 6.
Under fluidized state, native starch raw material is carried out heat treatment, why can solve to use accumulation state heating starch to prepare the technical problem existing for hard carbon microspheres at present, reason is as follows: first, when fluidized state, all starch granuless are all suspended in the carrier gas of motion, contact it is mutually disengaged and without phase mutual friction between starch granules, thus use the method for the treatment temperature improving heat stabilization to accelerate stabilisation process, also can't cause occurring melting also because of contacting with each other for a long time between starch granules, the problem such as caking；It addition, starch carries out under fluidized state heat treated, carrier gas surrounds starch granules and in its Surface runoff, thus not only rate of heat exchange is fast, makes material bed Temperature Distribution be more uniformly distributed, and reaction temperature is also readily obtained accurately control；And owing to mass transfer velocity is fast so that the light component product of the generation in heating process can quickly be taken out of, can avoid the generation of too much side reaction.This allows for mass transfer when preparing on a large scale, heat transfer problem has been resolved, thus the method is more suitable for large-scale production.Also the concordance of the hard carbon microsphere cathode material of prepared lithium ion battery, the first chemical property such as efficiency and cyclicity is made to get a promotion.
The present invention is with native starch as raw material, heated stabilisation, high temperature carbonization step prepares the hard carbon microsphere cathode material of starch base, in preparation process, application fluidized-bed reactor is as the stabilisation of starch material or carbonization processing device, under fluidized state, native starch is carried out heat stabilization or carbonization processes, such that it is able to improve stabilization reactions temperature, shorten the stabilization step time, improve preparation efficiency, also can solve the mass transfer in stabilization procedures simultaneously, heat transfer problem, it is easily achieved the large-scale production of starch base hard carbon microspheres material, and technique is simple, simultaneously, the hard carbon microsphere cathode material of lithium ion battery prepared by the method has the most excellent chemical property, as concordance is good, irreversible capacity is low, efficiency is high first, good cycle etc..
Embodiment 1
(1) natural black wheat starch raw material is put in fluidized-bed reactor, being continually fed into normal air makes natural black wheat starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.007 0.62cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 10 DEG C/min, when temperature reaches 180 DEG C, keep 100h that natural black wheat starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under helium atmosphere, 10h is kept after high temperature carbonization furnace being warming up to 700 DEG C with the heating rate of 20 DEG C/min, rye starch after stabilisation is carried out carbonization process, under helium atmosphere, it is cooled to room temperature after carbonization, obtains the hard carbon microsphere cathode material of rye starch base.
Embodiment 2
(1) native potato starch raw material is put in fluidized-bed reactor, being continually fed into nitrogen makes native potato starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.069 6.3cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when temperature reaches 245 DEG C, keep 8h that native potato starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under an argon atmosphere, 60min is kept after high temperature carbonization furnace being warming up to 1000 DEG C with the heating rate of 10 DEG C/min, potato starch after stabilisation is carried out carbonization process, it is cooled to room temperature after carbonization in a nitrogen atmosphere, obtains the hard carbon microsphere cathode material of potato starch base.
Embodiment 3
(1) native corn starch raw material is put in fluidized-bed reactor, being continually fed into dry air makes native corn starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.005 0.9cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when temperature reaches 220 DEG C, keep 36h that native corn starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under an argon atmosphere, keep 120min after high temperature carbonization furnace being warming up to 1100 DEG C with the heating rate of 10 DEG C/min, the corn starch after stabilisation is carried out carbonization process.After carbonization, protective atmosphere is switched to nitrogen, be cooled to room temperature in a nitrogen atmosphere, obtain the hard carbon microsphere cathode material of corn starch base.
Embodiment 4
(1) native rice starch raw material is put in fluidized-bed reactor, being continually fed into argon makes native rice starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.001 0.2m/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 2 DEG C/min, when temperature reaches 215 DEG C, keep 10h, continue to promote the temperature in fluidized-bed reactor with the heating rate of 1 DEG C/min, when temperature reaches 230 DEG C, keep 5h, continue to promote the temperature in fluidized-bed reactor with the heating rate of 1 DEG C/min, when temperature reaches 245 DEG C, keep 5h, native rice starch raw material is carried out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high-temperature rotary furnace, in a nitrogen atmosphere, 50min is kept after high temperature carbonization furnace being warming up to 1300 DEG C with the heating rate of 20 DEG C/min, rice starch after stabilisation is carried out carbonization process, it is cooled to room temperature after carbonization in a nitrogen atmosphere, obtains the hard carbon microsphere cathode material of rice starch base.
Embodiment 5
(1) native wheat starch raw material is put in fluidized-bed reactor, being continually fed into oxygen makes native wheat starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.003 4.3cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 2 DEG C/min, when reaching 230 DEG C when temperature, use linear temperature program, the temperature of fluidized-bed reactor is risen to 250 DEG C by 6h, and native wheat starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment; transfer the material in high-temperature rotary furnace; under an argon atmosphere; 1min is kept after high temperature carbonization furnace being warming up to 1800 DEG C with the heating rate of 30 DEG C/min; wheaten starch after stabilisation is carried out carbonization process; after carbonization, the protective atmosphere of high-temperature rotary furnace is switched to nitrogen, be cooled to room temperature in a nitrogen atmosphere, obtain the hard carbon microsphere cathode material of wheaten starch base.
Embodiment 6
(1) Native tapioca starch raw material is put in fluidized-bed reactor, being continually fed into sulfur hexafluoride makes Native tapioca starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 1.1 15.1cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when reaching 245 DEG C when temperature, keep 10h that Native tapioca starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, in a nitrogen atmosphere, at once lower the temperature after high temperature carbonization furnace being warming up to 1600 DEG C with the heating rate of 30 DEG C/min, it is cooled to room temperature in a nitrogen atmosphere, obtains the hard carbon microsphere cathode material of tapioca base.
Embodiment 7
(1) natural raw sweet potato starch is put in fluidized-bed reactor, being continually fed into nitrogen makes natural raw sweet potato starch be fluidized state (the gas speed scope in fluidized-bed reactor is 0.2 1.7cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when reaching 260 DEG C when temperature, use linear temperature program, the temperature of fluidized-bed reactor is risen to 280 DEG C by 1h, and natural raw sweet potato starch carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, in a nitrogen atmosphere, 6h is kept after high temperature carbonization furnace being warming up to 900 DEG C with the heating rate of 30 DEG C/min, sweet potato starch after stabilisation is carried out carbonization process, it is cooled to room temperature after carbonization in a nitrogen atmosphere, obtains the hard carbon microsphere cathode material of sweet potato starch base.
Embodiment 8
(1) native pea starch raw material is put in fluidized-bed reactor, being continually fed into oxygen makes native pea starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.01 3.6cm/s) with nitrogen mixture (volume ratio is 1:1) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when reaching 240 DEG C when temperature, keep 15h that native pea starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, the carrier gas being passed through fluidized-bed reactor is switched to nitrogen (the gas speed scope in fluidized-bed reactor is 0.02 4.3cm/s), in a nitrogen atmosphere, 20min is kept after temperature in fluidized-bed reactor being risen to 1150 DEG C with the heating rate of 5 DEG C/min, carry out carbonization process, it is cooled to room temperature after carbonization in a nitrogen atmosphere, obtains the hard carbon microsphere cathode material of pea starch base.
Embodiment 9
(1) native potato starch and Native tapioca starch 1:1 weight ratio raw material are put in fluidized-bed reactor, being continually fed into nitrogen makes native starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 5.9 20cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when reaching 250 DEG C when temperature, keep 20h that native starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, being continually fed into the starch after nitrogen makes stabilisation is fluidized state, keeps 30min simultaneously, carry out pre-carbonization process after temperature in fluidized-bed reactor being risen to 400 DEG C with the heating rate of 5 DEG C/min.After cooling, after pre-carbonization being processed, material is transferred to high temperature carbonization furnace, under an argon atmosphere, 3h is kept after high temperature carbonization furnace being warming up to 1500 DEG C with the heating rate of 15 DEG C/min, starch after pre-carbonization is carried out high temperature carbonization process, it is cooled to room temperature after carbonization under an argon atmosphere, obtains the hard carbon microsphere cathode material of composite starch.
Embodiment 10
(1) natural rubber fruit starch material is put in fluidized-bed reactor, being continually fed into carbon dioxide makes natural rubber fruit starch material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.05 3.1m/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 10 DEG C/min, when temperature reaches 200 DEG C, keep 250h that natural rubber fruit starch material is carried out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under neon atmosphere, 5min is kept after high temperature carbonization furnace being warming up to 1700 DEG C with the heating rate of 20 DEG C/min, rubber fruit starch after stabilisation is carried out carbonization process, under neon atmosphere, it is cooled to room temperature after carbonization, obtains the rubber fruit hard carbon microsphere cathode material of starch base.
Embodiment 11
(1) natural sorghum starch raw material is put in fluidized-bed reactor, being continually fed into water vapour makes natural sorghum starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.1 15cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 1 DEG C/min, when temperature reaches 280 DEG C, keep 30min that natural sorghum starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under xenon atmosphere, 8min is kept after high temperature carbonization furnace being warming up to 1600 DEG C with the heating rate of 20 DEG C/min, sorghum starch after stabilisation is carried out carbonization process, under xenon atmosphere, it is cooled to room temperature after carbonization, obtains the hard carbon microsphere cathode material of sorghum starch base.
Embodiment 12
(1) natural Semen Panici miliacei starch material is put in fluidized-bed reactor, being continually fed into neon makes natural Semen Panici miliacei starch material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.04 7.3cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 1 DEG C/min, when reaching 250 DEG C when temperature, use linear temperature program, the temperature of fluidized-bed reactor is risen to 280 DEG C by 50min, and natural Semen Panici miliacei starch material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under argon, hydrogen mixed gas atmosphere (argon is 19:1 with the volume ratio of hydrogen), keep 30h after high temperature carbonization furnace being warming up to 800 DEG C with the heating rate of 20 DEG C/min, the Semen Panici miliacei starch after stabilisation is carried out carbonization process.After carbonization, protective gas is switched to neon, under neon atmosphere, be cooled to room temperature, obtain the hard carbon microsphere cathode material of Semen Panici miliacei starch base.
Embodiment 13
(1) natural Semen phaseoli radiati starch material is put in fluidized-bed reactor, being continually fed into carbon tetrafluoride makes natural Semen phaseoli radiati starch material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.007 2.1cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 2 DEG C/min, when reaching 180 DEG C when temperature, use linear temperature program, the temperature of fluidized-bed reactor is risen to 280 DEG C by 150h, and natural Semen phaseoli radiati starch material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, the carrier gas being passed through fluidized-bed reactor is switched to nitrogen (the gas speed scope in fluidized-bed reactor is 0.01 3.5cm/s), keep 1h simultaneously after temperature in fluidized-bed reactor being risen to 350 DEG C with the heating rate of 5 DEG C/min, carry out pre-carbonization process.After cooling, after pre-carbonization being processed, material is transferred to high temperature carbonization furnace, under Krypton atmosphere, 6min is kept after high temperature carbonization furnace being warming up to 1200 DEG C with the heating rate of 15 DEG C/min, starch after stabilisation is carried out carbonization process, under Krypton atmosphere, it is cooled to room temperature after carbonization, obtains the hard carbon microsphere cathode material of green starch base.
Embodiment 14
(1) native potato starch raw material is put in fluidized-bed reactor, being continually fed into Krypton makes native potato starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 2.1 13.7cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 20 DEG C/min, when temperature reaches 120 DEG C, the temperature in fluidized-bed reactor is promoted again with the heating rate of 5 DEG C/min, when temperature reaches 195 DEG C, keep 200h that native potato starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment; transfer the material in high temperature carbonization furnace; under sulfur hexafluoride atmosphere; 1h is kept after high temperature carbonization furnace being warming up to 900 DEG C with the heating rate of 20 DEG C/min; potato starch after stabilisation is carried out carbonization process, after carbonization, protective gas is switched to nitrogen; it is cooled to room temperature in a nitrogen atmosphere, obtains the hard carbon microsphere cathode material of potato starch base.
Embodiment 15
(1) natural banana starch material is put in fluidized-bed reactor, being continually fed into argon makes natural banana starch material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.005 1.5cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 1 DEG C/min, when temperature reaches 250 DEG C, keep 50h that natural banana starch material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under Krypton atmosphere, 12h is kept after high temperature carbonization furnace being warming up to 1500 DEG C with the heating rate of 20 DEG C/min, banana starch after stabilisation is carried out carbonization process, under Krypton atmosphere, it is cooled to room temperature after carbonization, obtains the hard carbon microsphere cathode material of banana starch base.
Embodiment 16
(1) natural Faba bean starch raw material is put in fluidized-bed reactor, being continually fed into heptafluoro-propane makes natural Faba bean starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 5 7cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 1 DEG C/min, when temperature reaches 230 DEG C, keep 45h that natural Faba bean starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, the carrier gas being passed through fluidized-bed reactor is switched to argon (the gas speed scope in fluidized-bed reactor is 5.7 8.1cm/s), simultaneously with temperature in the heating rate lifting fluidized-bed reactor of 5 DEG C/min, when reaching 280 DEG C when temperature, use linear temperature program, the temperature of fluidized-bed reactor is risen to 290 DEG C by 5h, carries out pre-carbonization process.After cooling, after pre-carbonization being processed, material is transferred to high temperature carbonization furnace, under neon atmosphere, 30h is kept after high temperature carbonization furnace being warming up to 1400 DEG C with the heating rate of 15 DEG C/min, starch after stabilisation is carried out carbonization process, under neon atmosphere, it is cooled to room temperature after carbonization, obtains the hard carbon microsphere cathode material of Faba bean starch base.
Embodiment 17
(1) natural barley starch raw material is put in fluidized-bed reactor, being continually fed into carbon dioxide makes natural barley starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 0.005 0.7cm/s) with nitrogen mixture (volume ratio is 1:9) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when reaching 240 DEG C when temperature, keep 45h that natural barley starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, the carrier gas being passed through fluidized-bed reactor is switched to helium (the gas speed scope in fluidized-bed reactor is 0.02 1.3cm/s), under helium atmosphere, 13h is kept after temperature in fluidized-bed reactor being risen to 1150 DEG C with the heating rate of 5 DEG C/min, carry out carbonization process, under helium atmosphere, it is cooled to room temperature after carbonization, obtains the hard carbon microsphere cathode material of barley starch base.
Embodiment 18
(1) natural Lotus Root Starch raw material is put in fluidized-bed reactor, being continually fed into xenon makes natural Lotus Root Starch raw material be fluidized state (the gas speed scope in fluidized-bed reactor is 10 15.1cm/s) as carrier gas, the temperature in fluidized-bed reactor is promoted with the heating rate of 5 DEG C/min, when reaching 240 DEG C when temperature, keep 10h that natural Lotus Root Starch raw material carries out the stabilizing treatment of fluidized state；
(2) after stabilizing treatment, transfer the material in high temperature carbonization furnace, under helium atmosphere, at once lower the temperature after high temperature carbonization furnace being warming up to 1750 DEG C with the heating rate of 30 DEG C/min, under helium atmosphere, it is cooled to room temperature, obtains the hard carbon microsphere cathode material of Lotus Root Starch base.
Comparative example 1
Take native potato starch, be loaded in porcelain Noah's ark, Noah's ark be placed in tubular type retort.Under an argon atmosphere, it is warmed up to 230 DEG C with the heating rate of 5 DEG C/min, after keeping 60h to carry out stabilizing treatment, is warmed up to 1000 DEG C with the heating rate of 10 DEG C/min, after keeping 1 hour, is naturally cooling to room temperature, prepare hard carbon microspheres material.
Comparative example 2
(1) choosing ammonium chloride as catalyst, configuration concentration is the aqueous solution of the ammonium chloride of 5%；
(2) taking native potato starch is raw material, weighs potato starch and aqueous ammonium chloride solution according to shallow lake mass ratio 1:1, and will the two mix and blend 10min；
(3) use centrifugal method to be removed by the solvent in said mixture, then dry in drying baker in 45 DEG C, obtain the potato starch of impregnated catalyst；
(4) potato starch of impregnated catalyst is joined in heating furnace, rise to 200 DEG C with the heating rate of 5 DEG C/min in a nitrogen atmosphere and carry out stabilizing treatment 7h, then rise to 1000 DEG C with the heating rate of 10 DEG C/min and material is carried out carbonization process 1h, and it is cooled to room temperature in a nitrogen atmosphere, obtain starch-based carbon microsphere.
(5) by the materials'use acid elution that obtains 3 times, it is then used by 5 post-dryings of deionized water wash, i.e. obtains the lithium ion battery hard carbon microsphere cathode material of potato starch base prepared by catalysis method.
In comparative example 1, the preparation flow of carbon microspheres is relatively simple, only includes heat stabilization, high temperature carbonization and cooling step.Due to, during the method prepares carbon microspheres, starch material is that accumulation mode carries out zone heating in high temperature furnace, it is impossible to carry out stabilizing treatment at a higher temperature.Thus, the stabilization procedures at 230 DEG C extremely expends the time, up to 60h.In this example, intensification, carbonization constant temperature and cooling step about add up to 10h.Thus, using comparative example 1 method to prepare hard carbon microspheres needs to expend about 70h altogether.
In comparative example 2, owing to taking catalytic way to carry out stabilizing treatment, thus the preparation flow of entirety just becomes extremely complex.Concrete time-consuming situation is as follows: (1st) step is catalyst solution configuration, about expends 1h；(2nd) step be starch catalyst easily in dipping, about expend 1h；(3rd) step is solvent removal step, is divided into centrifugal and dries two operating processes, and centrifugal flow process about expends 1h, and dries flow process because drying temperature relatively low (temperature is too high easily causes native starch gelatinizing) required time is longer, about more than 12h；(4th) step is heating process, and required time is about 17h；(5th) step is pickling, washing process, needs altogether to clean, filter 8 times, and each required time is 1.5h, and drying time needs 12h, altogether 24h.So, using comparative example 2 method to prepare hard carbon microspheres needs to expend about 56h altogether.
In embodiment 2, (1st) step is stabilization step, and filler, temperature-rise period need 2h, stabilisation time to need 8h, cooling to need 1.5h, add up to 11.5h；(2nd) step is high temperature carbonization step, and material is transferred to high temperature carbonization furnace by fluidized-bed reactor needs 2h, and being warming up to 1000 DEG C probably needs 1.5h, high temperature carbonization 1h, cooling to need 7h, adds up to 11.5h.Thus, using embodiment 2 method to prepare hard carbon microspheres needs to expend about 23h altogether.
By above-mentioned contrast and with reference to Fig. 2 it can be seen that although the catalysis process that comparative example 2 is used can improve stabilisation efficiency, but because preparation flow is complex, thus preparation efficiency is more fairly obvious than the advantage of comparative example 1.Embodiment 2 have employed the heat stabilization processing method of fluidized state, hence it is evident that shortens heat stabilization and processes the time, does not the most increase too much preparation flow simultaneously, so using the starch base hard carbon microspheres preparation efficiency of the method to be significantly improved.In addition, it is necessary to it is emphasized that when being prepared on a large scale hard carbon microsphere cathode material with native starch for raw material, the advantage of the present invention then becomes apparent from.
| First charge-discharge reversible capacity | First charge-discharge irreversible capacity | Coulombic efficiency first | 50th discharge capacitance | |
| Embodiment 2 | 561mAh/g | 115mAh/g | 83% | 95% |
| Comparative example 1 | 557mAh/g | 185mAh/g | 75% | 90% |
| Comparative example 2 | 554mAh/g | 215mAh/g | 72% | 86% |
In addition to preparation efficiency is significantly improved, the chemical property of the hard carbon microsphere cathode material prepared by the inventive method is used to have also been obtained a certain degree of lifting.As shown above, comparing comparative example 1 and comparative example 2, the hard carbon microspheres material prepared by embodiment 2 has more excellent chemical property.In the case of reversible capacity is more or less the same, the irreversible capacity of hard carbon microsphere cathode material prepared by employing the inventive method has obtained good suppression, thus the most in hgher efficiency.Moreover, its cycle characteristics is the most excellent.This is because, carry out heat stabilization process in a fluidized bed reactor, mass-transfer efficiency is the highest, the light-component gas produced in stabilization procedures is short for time of contact with starch, the side reaction occurred is less, thus decrease the content of surface functional group in prepared hard carbon microspheres, it is suppressed that and the generation of hard carbon microsphere cathode material irreversible capacity, also make the cyclical stability of material promote.On the contrary, in comparative example 2, because dipping and repeatedly washing process so that more functional group is introduced in carbon microspheres surface, so its chemical property receives a certain degree of impact.
The principle of above-described embodiment only illustrative present invention and effect thereof; and the embodiment that part is used, for the person of ordinary skill of the art, without departing from the concept of the premise of the invention; can also make some deformation and improvement, these broadly fall into protection scope of the present invention.
Claims (14)
1. the preparation method of the hard carbon microsphere cathode material of lithium ion battery, it is characterised in that: comprise the steps
1) native starch raw material is put in fluidized-bed reactor, being continually fed into carrier gas makes native starch raw material be fluidized state, gradually promoting the temperature in fluidized-bed reactor, the heat stabilization that native starch raw material carries out in 180 280 DEG C of temperature ranges fluidized state processes；
2) under inert gas shielding, the starch after stabilizing treatment in step 1) is carried out the high temperature carbonization process of 700 1800 DEG C, after cooling, obtains the hard carbon microsphere cathode material of lithium rechargeable battery starch base.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 1, it is characterised in that in described step 1), the heat stabilization process time is 1 36h.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 1, it is characterized in that, described native starch is at least one in native potato starch, native corn starch, Native tapioca starch, natural sweet potato starch, native wheat starch, native rice starch or native pea starch.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 1, it is characterised in that the carrier gas in described step 1) is at least one in dry air, oxygen, nitrogen or argon.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 1, it is characterised in that the gas speed in fluidized-bed reactor of the carrier gas in described step 1) is 0.01 6.9cm/s.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 1, it is characterised in that the lifting of the fluidized-bed reactor temperature in described step 1) is to realize by the way of heating flows to fluidized-bed reactor carrier gas.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 1, it is characterised in that when heat stabilization processes in described step 1), in fluidized-bed reactor, temperature gradually rises.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 7, it is characterised in that the temperature in described fluidized-bed reactor raises with stabilizing treatment linearly.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 7, it is characterized in that, when in described step 1), starch is in fluidized state, carry out separating and sending back in fluidized-bed reactor by the starch granules of carrier gas entrained with by being arranged on the solid and gas segregation apparatus of fluidized-bed reactor rear end.
The preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery the most according to claim 9, it is characterised in that described solid and gas segregation apparatus is cyclone separator.
The preparation method of the 11. hard carbon microsphere cathode materials of a kind of lithium ion battery according to claim 1, it is characterized in that, described step 2) in high temperature carbonization process step, it is using noble gas as carrier gas, the starch after stabilisation is made in fluidized-bed reactor to keep fluidized state, and promote the temperature in fluidized-bed reactor to 280 450 DEG C, starch after stabilisation in step (1) carries out the pre-carbonization under fluidized state process, again pre-carbonization process material is put in high temperature carbonization furnace after cooling, the high temperature carbonization process of 700 1800 DEG C is carried out under inert atmosphere.
The preparation method of the 12. hard carbon microsphere cathode materials of a kind of lithium ion battery according to claim 1, it is characterized in that, described step 2) it is using noble gas as carrier gas, the starch after stabilisation is made in fluidized-bed reactor to keep fluidized state, and promote the temperature in fluidized-bed reactor to 700 1800 DEG C, stabilisation starch is carried out the high temperature carbonization under fluidized state and processes.
13. according to the preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery described in claim 1 or 11 or 12, it is characterised in that described step 2) in high temperature carbonization to process the time be 10min 10h.
14. according to the preparation method of the hard carbon microsphere cathode material of a kind of lithium ion battery described in claim 1 or 11 or 12, it is characterised in that described step 2) in noble gas be at least one in nitrogen or argon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107715774A (en) * | 2017-07-06 | 2018-02-23 | 东莞市创明电池技术有限公司 | Lithium battery slurry mixing method and solid powder premixing equipment |
| CN112678797A (en) * | 2020-12-23 | 2021-04-20 | 浙江阿佩克斯能源科技有限公司 | Rapid preparation method of hard carbon material |
| CN113224300A (en) * | 2021-04-15 | 2021-08-06 | 淄博火炬能源有限责任公司 | Preparation method of lead powder for negative electrode of lead-carbon battery |
| WO2023173772A1 (en) * | 2022-03-15 | 2023-09-21 | 广东邦普循环科技有限公司 | Preparation method for and use of hard carbon negative electrode material |
| CN119370825A (en) * | 2024-10-23 | 2025-01-28 | 清华大学 | A method and system for preparing carbonized particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715774A (en) * | 2017-07-06 | 2018-02-23 | 东莞市创明电池技术有限公司 | Lithium battery slurry mixing method and solid powder premixing equipment |
| CN112678797A (en) * | 2020-12-23 | 2021-04-20 | 浙江阿佩克斯能源科技有限公司 | Rapid preparation method of hard carbon material |
| CN113224300A (en) * | 2021-04-15 | 2021-08-06 | 淄博火炬能源有限责任公司 | Preparation method of lead powder for negative electrode of lead-carbon battery |
| CN113224300B (en) * | 2021-04-15 | 2022-07-29 | 淄博火炬能源有限责任公司 | Preparation method of lead powder for negative electrode of lead-carbon battery |
| WO2023173772A1 (en) * | 2022-03-15 | 2023-09-21 | 广东邦普循环科技有限公司 | Preparation method for and use of hard carbon negative electrode material |
| GB2618729B (en) * | 2022-03-15 | 2024-07-24 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method of hard carbon anode material and use thereof |
| CN119370825A (en) * | 2024-10-23 | 2025-01-28 | 清华大学 | A method and system for preparing carbonized particles |
| CN119370825B (en) * | 2024-10-23 | 2025-07-29 | 清华大学 | Preparation method and system of carbonized particles |
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|---|---|
| CN106006603B (en) | 2017-12-29 |
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