CN106006603B - A kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery - Google Patents
A kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery Download PDFInfo
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- CN106006603B CN106006603B CN201610337472.5A CN201610337472A CN106006603B CN 106006603 B CN106006603 B CN 106006603B CN 201610337472 A CN201610337472 A CN 201610337472A CN 106006603 B CN106006603 B CN 106006603B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 76
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 60
- 239000010406 cathode material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
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- 239000012298 atmosphere Substances 0.000 claims description 25
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- 229920001592 potato starch Polymers 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
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- 238000001816 cooling Methods 0.000 claims description 11
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
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- 229940100445 wheat starch Drugs 0.000 claims description 6
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- 238000006243 chemical reaction Methods 0.000 abstract description 14
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- 239000001307 helium Substances 0.000 description 7
- 229910052734 helium Inorganic materials 0.000 description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 7
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- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 7
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- 229910052743 krypton Inorganic materials 0.000 description 5
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018503 SF6 Inorganic materials 0.000 description 2
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- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery, belong to technical field of lithium ion battery negative, the present invention is using native starch as raw material, heated stabilisation, high temperature carbonization step prepare the hard carbon microsphere cathode material of starch base, in preparation process, using stabilisation or carbonization processing device of the fluidized-bed reactor as starch material, heat stabilization or charing process are carried out to native starch under fluidized state, this method can improve stabilization reactions temperature, shorten the stabilization step time, improve preparation efficiency；Can solve mass transfer, the heat transfer problem in stabilization procedures, it is easy to accomplish large-scale production；Meanwhile the chemical property of the hard carbon microsphere cathode material of lithium ion battery of this method preparation is also more excellent.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, and in particular to a kind of lithium ion battery hard charcoal microballoon is born
The preparation method of pole material.
Background technology
Lithium ion battery is because with energy density is high, power characteristic is good, operating voltage is high, have extended cycle life, pollution-free etc.
Advantage, make it before the many-sides such as portable electric appts, electric automobile, space technology, national defense industry have a wide range of applications
Scape, turn into the study hotspot widely paid close attention in recent years.
Carbon Materials are the preferable negative materials of lithium ion battery, and wherein graphite type material is that current most widely used charcoal is born
Pole material.In the last few years, advanced by leaps and bounds using the development of lithium ion battery as the portable electric appts of power supply, while lithium ion
Battery is also gradually being pushed to traffic dynamic field, so the requirement to lithium ion battery is also constantly improving.Along with this
The higher requirement of kind, graphite cathode material are got in the limitation than energy, power characteristic, cycle characteristics and security etc.
Invention is aobvious.
Hard carbon material has a higher specific capacity, superior fast charging and discharging ability, good cyclical stability and higher
The excellent chemical property such as ground security, it is to be hopeful very much to substitute one of negative material of conventional graphite class material.It is different
Initiation material and preparation method made from hard charcoal negative material pattern it is different, wherein the hard charcoal negative material of ball-type pattern because
With higher bulk density, low surface-to-volume than with higher mechanical performance, so as to be advantageous to hard carbon material electrochemistry
The lifting of performance, it is hot research direction.
At present, the hard carbon microsphere cathode material generally existing prices of raw materials of lithium ion battery are expensive, and non-renewable, environment is not
The problems such as friendly.In addition, the most complex process of the preparation method of hard charcoal microballoon, working condition is harsh, is not suitable for scale of mass production.
Thus, above mentioned problem significantly limit the commercialization process of the hard carbon microsphere cathode material of lithium ion battery.
Using starch as initiation material, handled by special process, the quasi ball-type shape for keeping starch granules can be made
The carbon microspheres material of looks.This is a kind of new carbon microspheres preparation method, be the advantage is that：First, starch material wide material sources,
It is renewable and environment-friendly；In addition, because avoiding the balling-up process of generally existing in carbon microspheres preparation process so that this method
Prepare the technical process very simple of carbon microspheres.
Document " Spherical hard carbon prepared from potato starch using as anode
In material for Li-ion batteries " (Materials Letters 65 (2011) 3368-3370), author
Starch base hard charcoal micro-sphere material is used as ion secondary battery cathode material lithium first, obtains the lithium with excellent chemical property
The hard carbon microsphere cathode material of ion battery.
Li Wenbin etc. is in Publication No. CN103647082A, and publication date is on March 19th, 2014, a kind of entitled " lithium
One kind is disclosed in the patent of invention of the preparation method of the hard carbon microsphere cathode material of ion secondary battery " at reduced pressure conditions, is led to
The method that overstabilization and carbonization process prepare the hard carbon microsphere cathode material of lithium ion battery, this method are produced after can suppressing charing
The caking tendency of thing, the irreversible capacity of hard carbon microsphere cathode material is reduced, also have one for the cyclical stability for lifting material
Fixed help.In the above method, in order to avoid foaming of the starch granules in carbonization process and agglomeration problems, it is necessary to take compared with
The mode of long-time heating stabilization processes is carried out at low temperature to starch, causes the preparation time of hard charcoal microballoon long.
For king Jin etc. in Publication No. CN102683661A, publication date is September in 2012 19, entitled " a kind of lithium from
In the patent of invention of the preparation method of sub- battery hard charcoal negative material ", one kind is disclosed using starch as raw material, through catalyst solution
Dipping, drying, heat stepwise, multiple pickling and drying and other steps, it is prepared for the side of the hard carbon microsphere cathode material of lithium ion battery
Method.In the invention, due to the effect of catalyst, when shortening the heat treatment in hard charcoal microballoon preparation process to a certain extent
Between.However, because wet starch can be gelatinized at 50-80 DEG C, therefore the drying in this method after catalyst solution impregnation steps
Process needs slowly to carry out at a lower temperature, adds the preparation time of carbon microspheres.In addition, more hypo acids after high temperature carbonization
Wash and drying steps, can also increase the preparation time of carbon microspheres, while active function groups, increase can be also introduced on carbon microspheres surface
The irreversible capacity of material and the cyclical stability for influenceing material.Thus, the method is difficult to be obviously improved starch base hard charcoal microballoon
Preparation efficiency, also whole preparation process can be made to become relatively complicated, run counter to starch base hard charcoal microsphere preparation technology technique letter
Single original intention.
The problem of starch base hard charcoal microballoon long preparation period, it is largely determined by stabilization procedures.With accumulation mode to material
Heated, because starch granules transfixion, higher stabilization temperature can cause the starch to contact with each other for a long time
Melt between particle simultaneously, cause caking phenomenon, so as to which scattered starch base hard charcoal micro-sphere material can not be made.It is above-mentioned in order to prevent
The occurrence of, it is necessary to take relatively low stabilization temperature to carry out stabilization processes to starch granules raw material.Relatively low stabilisation
Temperature, stabilisation process is delayed, it is therefore desirable to which the longer time can be only achieved required stabilization effect, to ensure in the later stage
Phenomena such as starch granules does not foam and melted simultaneously in high-temperature heating process.Although Above-mentioned catalytic method can reduce stabilisation temperature
Spend and accelerate stabilisation process, but also increase the complexity of carbon microspheres preparation technology simultaneously, and restrict to a certain extent
The performance of the hard carbon microsphere cathode material electrical property of starch base.
In addition, carrying out needing bigger inventory during technique amplification to above-mentioned preparation method, adopted at that time in the above method
Serious heat transfer and mass transfer problem can be brought by taking the mode of heating of stacked, and the performance of negative material is negatively affected.Put
Big stockpile, first, conduction of the heat in starch material heap in heating process can be hindered, cause in stockpile temperature not
Uniformity, the stabilization temperature control of raw starch was both not easy to, the uniformity of product can be influenceed again；In addition, it can also hinder to give birth to
Into the diffusion of light component material, increase the side reaction between light component material and carbon microspheres in heating process, cause material can not
The increase of inverse capacity simultaneously influences the cycle performance of material.
Sum up, technical problem underlying present in starch base hard charcoal microballoon cathode material preparation method includes at present：
First, preparation flow complexity, long preparation period, preparation efficiency are low；Second, technique amplification is difficult caused by heat transfer, mass transfer problem；
3rd, some steps in preparation process can have a negative impact to the chemical property of material.
The content of the invention
For problems of the prior art, it is an object of the invention to provide one kind using native starch as raw material system
The method of the hard carbon microsphere cathode material of lithium ion battery starch base of standby holding native starch particles primary morphology.
The technical solution adopted for the present invention to solve the technical problems is：A kind of hard carbon microsphere cathode material of lithium ion battery
Preparation method, comprise the following steps
1）Native starch raw material is put into fluidized-bed reactor, being continually fed into carrier gas makes native starch raw material be in fluidised form
Change state, the temperature in fluidized-bed reactor is gradually lifted, native starch raw material is carried out in 180-280 DEG C of temperature ranges
The heat stabilization processing of fluidized state；
2）Under inert gas shielding, to step 1）Starch after middle stabilization processes carries out 700-1800 DEG C of high temperature
Charing process, the hard carbon microsphere cathode material of lithium rechargeable battery starch base is obtained after cooling.
Preferably, the step 1）Middle heat stabilization processing time is 1-36h.
Preferably, described native starch is native potato starch, native corn starch, Native tapioca starch, day
At least one of right sweet potato starch, native wheat starch, native rice starch or native pea starch.
Preferably, the step 1）In carrier gas at least one of for dry air, oxygen, nitrogen or argon gas.
Preferably, the step 1）In gas velocity of the carrier gas in fluidized-bed reactor be 0.01-6.9cm/s.
Preferably, the step 1）In fluidized-bed reactor temperature lifting be by heating flow into fluidized-bed reaction
The mode of device carrier gas is realized.
Preferably, the step 1）Temperature gradually rises in fluidized-bed reactor during middle heat stabilization processing.
Preferably, the temperature in the fluidized-bed reactor raises with stabilization processes linearly.
Preferably, the step 1）When middle starch is in fluidized state, by being arranged on fluidized-bed reactor rear end
Solid and gas separator the starch granules of carrier gas entrained with is separated and sent back in fluidized-bed reactor, with improve stabilize
Step yield.
Preferably, described solid and gas separator is cyclone separator.
Further technical scheme is：The step 2）In high temperature carbonization processing step, be in stabilization processes step
1）After the completion of, using inert gas as carrier gas, the starch after being stabilized in fluidized-bed reactor is kept fluidized state,
And the temperature in fluidized-bed reactor is lifted to 280-450 DEG C, to step（1）Starch after middle stabilisation carries out fluidization shape
Pre- charing process under state, pre- charing process material is put into high temperature carbonization furnace again after cooling, carried out under inert atmosphere
700-1800 DEG C of high temperature carbonization processing.
Also can adopt the following technical scheme that：Described step 2）It is in stabilization processes step 1）After the completion of, with indifferent gas
Body makes the starch after being stabilized in fluidized-bed reactor keep fluidized state, and lift fluidized-bed reaction as carrier gas
Temperature in device is handled stabilizing the high temperature carbonization under starch progress fluidized state to 700-1800 DEG C.
Described step 2）In 700-1800 DEG C of high temperature carbonization processing time be 10min-10h.
Described step 2）In inert gas be at least one of nitrogen or argon gas.
The beneficial effects of the invention are as follows：
The present invention carries out stabilization processes in fluidized state to native starch, is separated from each other between starch granules, compared to heap
The heat stabilization process of cumuliformis state, melting between starch granules will not also occur even if raising stabilization processes temperature and and caking
Phenomenon.Thus, stabilization processes can be carried out at a higher temperature, can accelerate stabilisation process, greatly shortened at stabilisation
The time is managed, lifts preparation efficiency.
The present invention is stabilized or charing process in fluidized state to native starch, steady compared to the heating of stacking states
Fixedization or high temperature carbonization process, can avoid or mitigate occur because being contacted with each other between starch granules melt simultaneously, caking phenomenon.
The present invention is stabilized or charing process in fluidized state to native starch, and reactor temperature is uniform, keeps away
When having exempted from heat stabilization or the charing of stacking states because temperature is uneven and caused by homogeneity of product offset issue, institute can be lifted
Prepare the uniformity of the hard carbon microsphere cathode material of starch base.
The present invention is stabilized using fluidized-bed reactor to native starch particles or charing process prepares hard charcoal microballoon,
On the one hand, heat transfer and mass transfer problem when can solve to prepare hard carbon microsphere cathode material on a large scale, on the other hand, fluidized-bed reaction
The correlation technique of device is also more ripe, thus this method is easier to make for industrial amplification, is adapted to extensive prepare.
The present invention is stabilized or charing process in fluidized state to native starch, and mass transfer velocity is fast, avoids ease
The generation of the light-component gas gone out bad side reaction caused by being contacted with the long-time of starch particle surface, reduces product surface
Functional group content, the efficiency first or cycle characteristics of the hard carbon microsphere cathode material of prepared starch base can be lifted.
Brief description of the drawings
Fig. 1 is fluidized bed reaction schematic diagram used in patent of the present invention；
Fig. 2 is the electronic scanner microscope of the hard carbon microsphere cathode material of farina base prepared using the inventive method
Photo.
Each reference is：1-fluidized-bed reactor, 2-temperature controller, 3-outer wall heater, 4-raw material add
Material mouth, 5-air distribution plate, 6-carrier gas heater, 7-temperature sensor, 8-solid-gas separator.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of fluidized bed reaction used in the present invention, and the figure is only fluidized bed reaction
Schematic diagram, to illustrate embodiments of the present invention, it is impossible to represent the fluidized bed reaction of actual use, actual use completely
Fluidized bed reaction be also not necessarily limited to preparation facilities shown in schematic diagram.
The preparation facilities includes fluidized-bed reactor 1 and the outer wall heater 3 being coated on fluidized-bed reactor 1,
The described upper and lower side of fluidized-bed reactor 1 is connected to blast pipe and air inlet pipe, and being provided with carrier gas in described air inlet pipe adds
Hot device 6, is connected to charge pipe and drainage conduit at left and right sides of the described lower end of fluidized-bed reactor 1, on described charge pipe
Raw materials mouth 4 is provided with, discharging opening is provided with described drainage conduit, is connected between described drainage conduit and blast pipe solid
Gas separating device 8, temperature sensor 7 is provided with described fluidized-bed reactor 1, temperature is connected with described temperature sensor 7
Controller 2 is spent, described outer wall heater 3 and carrier gas heater 6 are connected with temperature controller 2, described fluidized-bed reaction
The air distribution plate 5 being additionally provided with device 1 below charge pipe and drainage conduit.
Preparation facilities of the present invention passes through temperature sensor 7, temperature controller 2, outer wall heater 3 and carrier gas heater 6
Temperature in common monitoring, control fluidized-bed reactor：Temperature sensor 7 passes the temperature signal inside fluidized-bed reactor 1
Temperature controller 2 is given, temperature controller 2 is according to the temperature signal monitored, to outer wall heater 3 or carrier gas heater 6
Thermal control signals are sent, so as to realize the regulation to temperature in reactor 1.
In lithium rechargeable battery hard charcoal microballoon preparation process, first by raw starch（Raw starch is native starch, and
Starches are not particularly limited, can such as use natural grain kind of starch, rhizome kind of starch, bean starch or fruit kind of starch,
Using native potato starch, cornstarch, tapioca, sweet potato starch, wheaten starch, rice starch or pea starch as excellent
Choosing）It is added to from charge door 4 in fluidized-bed reactor 1（Fluidized-bed reactor 1 is carried out under fluidized state steady by starch
The reaction vessel of fixedization, pre- charing or high temperature carbonization processing）；It is passed through carrier gas（Carrier gas can be it is any it is nontoxic, harmless, do not pollute
One or more in the gas of environment, preferably dry air, oxygen, nitrogen or argon gas）, carrier gas is after carrier gas heater 6
Enter reactor from fluidized-bed reactor bottom, after air distribution plate 5 is uniformly distributed, raw starch is kicked up, it is in fluidization to make it
State, i.e. starch granules are suspended in the carrier gas of motion, contact are mutually disengaged between starch granules and without phase mutual friction.
When starch is in fluidized state, part material can be more by carrier gas picks, the raw material of the bigger entrainment of carrier gas gas velocity.
Therefore, at least one embodiment of the invention, gas-solid separating device 8 as shown in the figure are set in the end of fluidized-bed reactor 1, will
The starch granules of entrainment is sent back in fluidized-bed reactor 1 after being separated from outlet carrier gas to be continued to participate in reaction.In the present invention at least
In one embodiment, gas-solid separating device 8 uses cyclone separator.In addition, at least one embodiment of the invention, gas-solid point
From device 8 be cyclone separator beyond other kinds of gas-solid separating device, such as dedusting airbag.
As described in art solutions of the present invention, in lithium ion secondary battery hard-carbon microsphere negative electrode preparation process,
It can carry out 180-280 DEG C of stabilization processes in a fluidized bed reactor, 280-450 DEG C of pre- charing process or 700-
1800 DEG C of high temperature carbonization processing.During stabilization processes, preferably carrier gas heater 6 heats to flowing through carrier gas（At this
Invent at least one embodiment, temperature in fluidized-bed reactor is lifted by the way of carrier gas heater heats carrier gas；Equally
Other mode of heatings lifting reactor temperature can be used, such as uses outer wall heater at least one embodiment of the invention
The mode of heating lifts temperature in fluidized-bed reactor）, temperature in fluidized-bed reactor 1 is gradually risen, so as to meet stabilization
Change temperature requirement.If carbonized in advance in fluidized-bed reactor 1 or high temperature carbonization handle when, use carrier gas heater 6 merely
Possibly temperature in fluidized-bed reactor 1 target temperature can not be promoted to, then outer wall heater 3 and carrier gas heater can be passed through
Temperature in 6 common lifting fluidized-bed reactors 1.
Native starch raw material is heat-treated under fluidized state, why can solve using accumulation state to add at present
Hot starch prepares the technical problem present in hard charcoal microballoon, and reason is as follows：First, in fluidized state, all starch granules
It is suspended in the carrier gas of motion, contact is mutually disengaged between starch granules and without phase mutual friction, thus it is steady using heating is improved
Surely the method for the treatment temperature changed accelerates stabilisation process, can't also cause between starch granules because contact with each other for a long time and
Appearance melt simultaneously, caking the problems such as；In addition, heating under fluidized state to starch, carrier gas surrounds starch granules simultaneously
In its surface flow, thus not only rate of heat exchange is fast, is more uniformly distributed material bed Temperature Distribution, and reaction temperature is also easy to be obtained
To accurate control；And because mass transfer velocity is fast so that the caused light component product in heating process can quickly be taken out of,
The generation of excessive side reaction can be avoided.Mass transfer, heat transfer problem when this allows for preparing on a large scale are resolved, thus this method
It is more suitable for large-scale production.Also so that the uniformity of the hard carbon microsphere cathode material of prepared lithium ion battery, first efficiency
And the chemical property such as cyclicity gets a promotion.
For the present invention using native starch as raw material, heated stabilisation, high temperature carbonization step prepare starch base hard charcoal microballoon
Negative material, in preparation process, using stabilisation or carbonization processing device of the fluidized-bed reactor as starch material, flowing
Heat stabilization or charing process are carried out to native starch under state state, so as to improve stabilization reactions temperature, shortened
The stabilization step time, preparation efficiency is improved, while can also solve mass transfer, the heat transfer problem in stabilization procedures, it is easy to accomplish
The large-scale production of starch base hard charcoal micro-sphere material, and technique is simple, meanwhile, lithium ion battery hard charcoal prepared by this method is micro-
Ball negative material has more excellent chemical property, as uniformity is good, irreversible capacity is low, efficiency high, cyclicity first
It can wait well.
Embodiment 1
（1）Natural rye starch raw material is put into fluidized-bed reactor, be continually fed into normal air makes as carrier gas
Natural rye starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.007-0.62cm/s）, with
Temperature in 10 DEG C/min heating rate lifting fluidized-bed reactor, when temperature reaches 180 DEG C, keeps 100h to natural black
Wheat starch raw material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under helium atmosphere, with 20 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 700 DEG C after keep 10h, to after stabilisation rye starch carry out charing process,
Normal temperature is cooled under helium atmosphere after charing, obtains the hard carbon microsphere cathode material of rye starch base.
Embodiment 2
（1）Native potato starch raw material is put into fluidized-bed reactor, be continually fed into nitrogen makes day as carrier gas
Right farina raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.069-6.3cm/s）, with 5
DEG C/min heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 245 DEG C, keep 8h to Native potato
Starch material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under an argon atmosphere, with 10 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1000 DEG C after keep 60min, the farina after stabilisation is carbonized
Processing, is cooled to normal temperature, obtains the hard carbon microsphere cathode material of farina base in a nitrogen atmosphere after charing.
Embodiment 3
（1）Native corn starch raw material is put into fluidized-bed reactor, be continually fed into dry air makes as carrier gas
Native corn starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.005-0.9cm/s）, with 5
DEG C/min heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 220 DEG C, keep 36h to natural corn
Starch material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under an argon atmosphere, with 10 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1100 DEG C after keep 120min, the cornstarch after stabilisation is carried out at charing
Reason.After charing, protective atmosphere is switched into nitrogen, is cooled to normal temperature in a nitrogen atmosphere, obtain corn starch base hard charcoal microballoon
Negative material.
Embodiment 4
（1）Native rice starch raw material is put into fluidized-bed reactor, be continually fed into argon gas makes naturally as carrier gas
Rice starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.001-0.2m/s）, with 2 DEG C/min
Heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 215 DEG C, keep 10h, continue with 1 DEG C/min's
Temperature in heating rate lifting fluidized-bed reactor, when temperature reaches 230 DEG C, keeps 5h, continues with 1 DEG C/min heating
Temperature in speed lifting fluidized-bed reactor, when temperature reaches 245 DEG C, keeps 5h, native rice starch raw material is carried out
The stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high-temperature rotary furnace, in a nitrogen atmosphere, with 20 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1300 DEG C after keep 50min, the rice starch after stabilisation is carried out at charing
Reason, is cooled to normal temperature, obtains the hard carbon microsphere cathode material of rice starch base in a nitrogen atmosphere after charing.
Embodiment 5
（1）Native wheat starch raw material is put into fluidized-bed reactor, be continually fed into oxygen makes naturally as carrier gas
Raw Wheat Starch is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.003-4.3cm/s）, with 2 DEG C/
Temperature in min heating rate lifting fluidized-bed reactor, when temperature reaches 230 DEG C, using linear temperature program, 6h
The temperature of fluidized-bed reactor is risen to 250 DEG C, the stabilization processes of fluidized state are carried out to native wheat starch raw material；
（2）After stabilization processes, transfer the material in high-temperature rotary furnace, under an argon atmosphere, with 30 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1800 DEG C after keep 1min, the wheaten starch after stabilisation is carried out at charing
Reason, is switching to nitrogen by the protective atmosphere of high-temperature rotary furnace after charing, is being cooled to normal temperature in a nitrogen atmosphere, obtains wheat shallow lake
The hard carbon microsphere cathode material of powder base.
Embodiment 6
（1）Native tapioca starch raw material is put into fluidized-bed reactor, be continually fed into sulfur hexafluoride makes as carrier gas
Native tapioca starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 1.1-15.1cm/s）, with 5
DEG C/min heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 245 DEG C, keeping 10h to natural wood
Sweet potato starch raw material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, in a nitrogen atmosphere, with 30 DEG C/min
Heating rate high temperature carbonization furnace be warming up to after 1600 DEG C cooled at once, be cooled to normal temperature in a nitrogen atmosphere, obtain cassava
The hard carbon microsphere cathode material of starch base.
Embodiment 7
（1）Natural raw sweet potato starch is put into fluidized-bed reactor, be continually fed into nitrogen makes naturally as carrier gas
Raw sweet potato starch is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.2-1.7cm/s）, with 5 DEG C/min
Heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 260 DEG C, using linear temperature program, 1h will
The temperature of fluidized-bed reactor rises to 280 DEG C, and the stabilization processes of fluidized state are carried out to natural raw sweet potato starch；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, in a nitrogen atmosphere, with 30 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 900 DEG C after keep 6h, to after stabilisation sweet potato starch carry out charing process, charcoal
Normal temperature is cooled to after change 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 into fluidized-bed reactor, is continually fed into oxygen and nitrogen mixture（Body
Product is than being 1：1）Native pea starch raw material is set to be in fluidized state as carrier gas（Gas velocity scope in fluidized-bed reactor is
0.01—3.6cm/s）, with the temperature in 5 DEG C/min heating rate lifting fluidized-bed reactor, reaching 240 DEG C when temperature
When, keep 15h to carry out the stabilization processes of fluidized state to native pea starch raw material；
（2）After stabilization processes, the carrier gas for being passed through fluidized-bed reactor is switched into nitrogen（In fluidized-bed reactor
Interior gas velocity scope is 0.02-4.3cm/s）, in a nitrogen atmosphere, with 5 DEG C/min heating rate by fluidized-bed reactor
Temperature keeps 20min after rising to 1150 DEG C, carry out charing process, be cooled to normal temperature after charing in a nitrogen atmosphere, obtain pea
The hard carbon microsphere cathode material of starch base.
Embodiment 9
（1）By native potato starch and Native tapioca starch 1：1 weight is put into fluidized-bed reactor than raw material, is held
It is continuous to be passed through nitrogen and make native starch raw material be in fluidized state as carrier gas（Gas velocity scope in fluidized-bed reactor is
5.9—20cm/s）, with the temperature in 5 DEG C/min heating rate lifting fluidized-bed reactor, when temperature reaches 250 DEG C,
20h is kept to carry out the stabilization processes of fluidized state to native starch raw material；
（2）After stabilization processes, being continually fed into nitrogen makes the starch after stabilisation be in fluidized state, while with 5
DEG C/min heating rate keeps 30min after temperature in fluidized-bed reactor is risen into 400 DEG C, carry out pre- charing process.Cooling
Afterwards, material after pre- charing process is transferred to high temperature carbonization furnace, under an argon atmosphere, with 15 DEG C/min heating rate by high temperature
Retort keeps 3h after being warming up to 1500 DEG C, high temperature carbonization processing is carried out to the starch after pre- charing, in argon gas atmosphere after charing
Under be cooled to normal temperature, obtain the hard carbon microsphere cathode material of composite starch.
Embodiment 10
（1）Natural rubber fruit starch material is put into fluidized-bed reactor, be continually fed into carbon dioxide makes as carrier gas
Natural rubber fruit starch material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.05-3.1m/s）, with 10
DEG C/min heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 200 DEG C, keep 250h to natural rubber fruit
Starch material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under neon atmosphere, with 20 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1700 DEG C after keep 5min, the rubber fruit starch after stabilisation is carried out at charing
Reason, is cooled to normal temperature under neon atmosphere after charing, obtains the hard carbon microsphere cathode material of rubber fruit starch base.
Embodiment 11
（1）Natural sorghum starch raw material is put into fluidized-bed reactor, be continually fed into water vapour makes day as carrier gas
Right sorghum starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.1-15cm/s）, with 1 DEG C/min
Heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 280 DEG C, keep 30min to natural sorghum starch
Raw material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under xenon atmosphere, with 20 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1600 DEG C after keep 8min, the sorghum starch after stabilisation is carried out at charing
Reason, is cooled to normal temperature under xenon atmosphere after charing, obtains the hard carbon microsphere cathode material of sorghum starch base.
Embodiment 12
（1）Natural milled glutinous broomcorn millet starch material is put into fluidized-bed reactor, be continually fed into neon makes naturally as carrier gas
Milled glutinous broomcorn millet starch material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.04-7.3cm/s）, with 1 DEG C/min
Heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 250 DEG C, using linear temperature program, 50min
The temperature of fluidized-bed reactor is risen to 280 DEG C, the stabilization processes of fluidized state are carried out to natural milled glutinous broomcorn millet starch material；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, in argon gas, hydrogen mixed gas atmosphere
（The volume ratio of argon gas and hydrogen is 19：1）Under, protected after high temperature carbonization furnace is warming up into 800 DEG C with 20 DEG C/min heating rate
30h is held, charing process is carried out to the milled glutinous broomcorn millet starch after stabilisation.After charing, protective gas is switched into neon, in neon atmosphere
Under be cooled to normal temperature, obtain the hard carbon microsphere cathode material of milled glutinous broomcorn millet starch base.
Embodiment 13
（1）Natural mung bean starch material is put into fluidized-bed reactor, be continually fed into carbon tetrafluoride makes as carrier gas
Natural mung bean starch material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.007-2.1cm/s）, with 2
DEG C/min heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 180 DEG C, using linear temperature increase journey
The temperature of fluidized-bed reactor is risen to 280 DEG C by sequence, 150h, and the stabilisation of fluidized state is carried out to natural mung bean starch material
Processing；
（2）After stabilization processes, the carrier gas for being passed through fluidized-bed reactor is switched into nitrogen（In fluidized-bed reactor
Interior gas velocity scope is 0.01-3.5cm/s）, while risen to temperature in fluidized-bed reactor with 5 DEG C/min heating rate
1h is kept after 350 DEG C, carries out pre- charing process.After cooling, material after pre- charing process is transferred to high temperature carbonization furnace, in Krypton
Under atmosphere, 6min is kept after high temperature carbonization furnace is warming up into 1200 DEG C with 15 DEG C/min heating rate, to the shallow lake after stabilisation
Powder carries out charing process, is cooled to normal temperature under Krypton atmosphere after charing, obtains the hard carbon microsphere cathode material of green starch base.
Embodiment 14
（1）Native potato starch raw material is put into fluidized-bed reactor, be continually fed into Krypton makes day as carrier gas
Right farina raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 2.1-13.7cm/s）, with 20
DEG C/min heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 120 DEG C, then the heating with 5 DEG C/min
Temperature in speed lifting fluidized-bed reactor, when temperature reaches 195 DEG C, keeps 200h to enter native potato starch raw material
The stabilization processes of row fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under sulfur hexafluoride atmosphere, with 20 DEG C/
Min heating rate keeps 1h after high temperature carbonization furnace is warming up into 900 DEG C, and the farina after stabilisation is carried out at charing
Reason, after charing, switches to nitrogen by protective gas, is cooled to normal temperature in a nitrogen atmosphere, it is micro- to obtain farina base hard charcoal
Ball negative material.
Embodiment 15
（1）Natural banana starch material is put into fluidized-bed reactor, be continually fed into argon gas makes naturally as carrier gas
Banana starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 0.005-1.5cm/s）, with 1 DEG C/
Temperature in min heating rate lifting fluidized-bed reactor, when temperature reaches 250 DEG C, keeps 50h to natural banana starch
Raw material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under Krypton atmosphere, with 20 DEG C/min
Heating rate high temperature carbonization furnace is warming up to 1500 DEG C after keep 12h, to after stabilisation banana starch carry out charing process,
Normal temperature is cooled under Krypton atmosphere after charing, obtains the hard carbon microsphere cathode material of banana starch base.
Embodiment 16
（1）Natural Faba bean starch raw material is put into fluidized-bed reactor, be continually fed into heptafluoro-propane makes as carrier gas
Natural Faba bean starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 5-7cm/s）, with 1 DEG C/min
Heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 230 DEG C, keep 45h former to natural Faba bean starch
Material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, the carrier gas for being passed through fluidized-bed reactor is switched into argon gas（In fluidized-bed reactor
Interior gas velocity scope is 5.7-8.1cm/s）, while temperature in fluidized-bed reactor is lifted with 5 DEG C/min heating rate,
When temperature reaches 280 DEG C, using linear temperature program, the temperature of fluidized-bed reactor is risen to 290 DEG C by 5h, is carbonized in advance
Processing.After cooling, material after pre- charing process is transferred to high temperature carbonization furnace, under neon atmosphere, with 15 DEG C/min heating
Speed keeps 30h after high temperature carbonization furnace is warming up into 1400 DEG C, charing process is carried out to the starch after stabilisation, in neon after charing
Normal temperature is cooled under gas atmosphere, obtains the hard carbon microsphere cathode material of Faba bean starch base.
Embodiment 17
（1）Natural barley starch raw material is put into fluidized-bed reactor, carbon dioxide is continually fed into and is mixed with nitrogen
Gas（Volume ratio is 1：9）Natural barley starch raw material is set to be in fluidized state as carrier gas（Gas velocity in fluidized-bed reactor
Scope is 0.005-0.7cm/s）, with the temperature in 5 DEG C/min heating rate lifting fluidized-bed reactor, reached when temperature
During to 240 DEG C, 45h is kept to carry out the stabilization processes of fluidized state to natural barley starch raw material；
（2）After stabilization processes, the carrier gas for being passed through fluidized-bed reactor is switched into helium（In fluidized-bed reactor
Interior gas velocity scope is 0.02-1.3cm/s）, under helium atmosphere, with 5 DEG C/min heating rate by fluidized-bed reactor
Temperature keeps 13h after rising to 1150 DEG C, carry out charing process, normal temperature is cooled under helium atmosphere after charing, obtains barley shallow lake
The hard carbon microsphere cathode material of powder base.
Embodiment 18
（1）Natural Lotus Root Starch raw material is put into fluidized-bed reactor, be continually fed into xenon makes naturally as carrier gas
Lotus Root Starch raw material is in fluidized state（Gas velocity scope in fluidized-bed reactor is 10-15.1cm/s）, with 5 DEG C/min
Heating rate lifting fluidized-bed reactor in temperature, when temperature reaches 240 DEG C, keep 10h to natural Lotus Root Starch
Raw material carries out the stabilization processes of fluidized state；
（2）After stabilization processes, transfer the material in high temperature carbonization furnace, under helium atmosphere, with 30 DEG C/min
Heating rate high temperature carbonization furnace be warming up to after 1750 DEG C cooled at once, be cooled to normal temperature under helium atmosphere, obtain lotus rhizome
The hard carbon microsphere cathode material of starch base.
Comparative example 1
Native potato starch is taken, is loaded into porcelain Noah's ark, Noah's ark is placed into tubular type retort.In argon gas atmosphere
Under, 230 DEG C are warming up to 5 DEG C/min heating rate, after keeping 60h to carry out stabilization processes, with 10 DEG C/min heating speed
Rate is warming up to 1000 DEG C, after being kept for 1 hour, is naturally cooling to normal temperature, and hard charcoal micro-sphere material is made.
Comparative example 2
（1）Ammonium chloride is chosen as catalyst, configuration concentration is the aqueous solution of 5% ammonium chloride；
（2）It is raw material to take native potato starch, according to shallow lake mass ratio 1：1 weighs farina and ammonium chloride solution
Liquid, and the two is mixed into 10min；
（3）The solvent in said mixture is removed using centrifugal method, then dries, obtains in drying box in 45 DEG C
The farina of impregnated catalyst；
（4）The farina of impregnated catalyst is added in heating furnace, in a nitrogen atmosphere with 5 DEG C/min heating
Speed rises to 200 DEG C of progress stabilization processes 7h, and then rise to 1000 DEG C with 10 DEG C/min heating rate carries out charcoal to material
Change processing 1h, and be cooled to normal temperature in a nitrogen atmosphere, obtain starch-based carbon microsphere.
（5）By obtained materials'use acid elution 3 times, then make to dry after being washed with deionized 5 times, that is, be catalyzed
The hard carbon microsphere cathode material of lithium ion battery farina base prepared by method.
In comparative example 1, the preparation flow of carbon microspheres is relatively simple, only includes heat stabilization, high temperature carbonization and cooling step
Suddenly.Because during this method prepares carbon microspheres, starch material is that accumulation mode carries out heat stepwise in high temperature furnace, can not
Stabilization processes are carried out at a higher temperature.Thus, the stabilization procedures at 230 DEG C extremely expend the time, up to 60h.This
The about total 10h of heating, charing constant temperature and cooling step in example.Thus, prepare hard charcoal microballoon using the method for comparative example 1 needs altogether
Expend about 70h.
In comparative example 2, due to taking catalytic way to carry out stabilization processes, thus overall preparation flow just becomes very
It is complicated.Specifically time-consuming situation is as follows：The（1）Step configures for catalyst solution, about expends 1h；The（2）Step is that starch exists
Catalyst is easily middle to be impregnated, and about expends 1h；The（3）Walk as solvent removal step, be divided into two operating processes of centrifugation and drying,
Centrifugation flow about expends 1h, and dries flow because drying temperature is relatively low（Temperature is too high easily to cause native starch to be gelatinized）Taken
Between longer, about more than 12h；The（4）Step is heating process, and required time is 17h or so；The（5）Step is pickling, water
Wash journey, need to clean altogether, filter 8 times, required time is 1.5h every time, and drying time needs 12h, common 24h.So use
The method of comparative example 2, which prepares hard charcoal microballoon, to be needed to expend about 56h altogether.
In embodiment 2, the（1）Walk needs 2h for stabilization step, filler, temperature-rise period, and the stabilisation time needs 8h, drops
Temperature needs 1.5h, adds up to 11.5h；The（2）Walk and high temperature carbonization furnace is transferred to by fluidized-bed reactor for high temperature carbonization step, material
2h is needed, being warming up to 1000 DEG C probably needs 1.5h, high temperature carbonization 1h, and cooling needs 7h, adds up to 11.5h.Thus, using implementation
The method of example 2, which prepares hard charcoal microballoon, to be needed to expend about 23h altogether.
By above-mentioned contrast and reference picture 2 as can be seen that although catalysis process can improve surely used by comparative example 2
Surely efficiency is changed, but because preparation flow is complex, thus preparation efficiency is not more fairly obvious than the advantage of comparative example 1.Implement
Example 2 employs the heat stabilization processing method of fluidized state, hence it is evident that shortens heat stabilization processing time, while does not also have
Having increases excessive preparation flow, so being significantly improved using the starch base hard charcoal microballoon preparation efficiency of this method.In addition,
It is important to note that when being prepared on a large scale hard carbon microsphere cathode material as raw material using native starch, advantage of the invention
Then become apparent.
| 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, using the electrification of the hard carbon microsphere cathode material prepared by the inventive method
Learn performance and also obtain a certain degree of lifting.As shown above, compared to comparative example 1 and comparative example 2, prepared by embodiment 2
Hard charcoal micro-sphere material has more excellent chemical property.In the case where reversible capacity is more or less the same, using present invention side
The irreversible capacity of hard carbon microsphere cathode material prepared by method has obtained good suppression, thus more efficient first.Not only such as
This, its cycle characteristics is also more excellent.Because heat stabilization processing, mass-transfer efficiency are carried out in a fluidized bed reactor
Very high, caused light-component gas and starch time of contact are short in stabilization procedures, and the side reaction occurred is less, so as to subtract
Lack the content of surface functional group in prepared hard charcoal microballoon, it is suppressed that the generation of hard carbon microsphere cathode material irreversible capacity,
Also so that the cyclical stability of material has been lifted.On the contrary, in comparative example 2, because dipping and multiple washing process so that more
More functional groups is introduced in carbon microspheres surface, so its chemical property receives a certain degree of influence.
The above-described embodiments merely illustrate the principles and effects of the present invention, and the embodiment that part uses, for
For one of ordinary skill in the art, without departing from the concept of the premise of the invention, can also make it is some deformation and
Improve, these belong to protection scope of the present invention.
Claims (13)
- A kind of 1. preparation method of the hard carbon microsphere cathode material of lithium ion battery, it is characterised in that：Comprise the following steps1）Native starch raw material is put into fluidized-bed reactor, being continually fed into carrier gas makes native starch raw material be in fluidization shape State, the temperature in fluidized-bed reactor is gradually lifted, fluidised form is carried out to native starch raw material in 180-280 DEG C of temperature ranges The heat stabilization processing of change state；2）Under inert gas shielding, to step 1）Starch after middle stabilization processes carries out 700-1800 DEG C of high temperature carbonization Processing, obtains the hard carbon microsphere cathode material of lithium rechargeable battery starch base after cooling.
- A kind of 2. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, it is characterised in that The step 1）Middle heat stabilization processing time is 1-36h.
- A kind of 3. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, it is characterised in that Described native starch is native potato starch, native corn starch, Native tapioca starch, natural sweet potato starch, natural small At least one of wheat starch, native rice starch or native pea starch.
- A kind of 4. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, it is characterised in that The step 1）In carrier gas at least one of for dry air, oxygen, nitrogen or argon gas.
- A kind of 5. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, it is characterised in that The step 1）In fluidized-bed reactor temperature lifting be heating flow into fluidized-bed reactor carrier gas by way of realize.
- A kind of 6. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, it is characterised in that The step 1）Temperature gradually rises in fluidized-bed reactor during middle heat stabilization processing.
- A kind of 7. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 6, it is characterised in that Temperature in the fluidized-bed reactor raises with stabilization processes linearly.
- A kind of 8. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 6, it is characterised in that The step 1）When middle starch is in fluidized state, it will be carried by the solid and gas separator for being arranged on fluidized-bed reactor rear end The starch granules of gas entrained with is separated and sent back in fluidized-bed reactor.
- A kind of 9. preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 8, it is characterised in that Described solid and gas separator is cyclone separator.
- 10. a kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, its feature exist In the step 2）In high temperature carbonization processing step, be using inert gas as carrier gas, make to stabilize in fluidized-bed reactor Starch afterwards keeps fluidized state, and lifts the temperature in fluidized-bed reactor to 280-450 DEG C, to step（1）In Starch after stabilisation carries out the pre- charing process under fluidized state, and pre- charing process material is put into high temperature again after cooling In retort, 700-1800 DEG C of high temperature carbonization processing is carried out under inert atmosphere.
- 11. a kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1, its feature exist In described step 2）It is using inert gas as carrier gas, the starch after being stabilized in fluidized-bed reactor is kept stream State state, and the temperature in fluidized-bed reactor is lifted to 700-1800 DEG C, carried out to stabilizing starch under fluidized state High temperature carbonization processing.
- 12. a kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1 or 10 or 11, its It is characterised by, described step 2）The high temperature charing process time is 10min -10h.
- 13. a kind of preparation method of the hard carbon microsphere cathode material of lithium ion battery according to claim 1 or 10 or 11, its It is characterised by, described step 2）In inert gas be at least one of nitrogen or argon gas.
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| GB2618729A (en) * | 2022-03-15 | 2023-11-15 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method of hard carbon anode material and use thereof |
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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 |
| 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 |
| CN119370825B (en) * | 2024-10-23 | 2025-07-29 | 清华大学 | Preparation method and system of carbonized particles |
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| GB853828A (en) * | 1958-07-21 | 1960-11-09 | Staley Mfg Co A E | Methods for treating starch |
| CN103663450B (en) * | 2013-12-19 | 2016-03-16 | 中国科学院过程工程研究所 | A kind of high-specific surface area carbosphere and preparation method thereof |
| CN103647082B (en) * | 2013-12-24 | 2016-05-04 | 中国船舶重工集团公司第七一二研究所 | The preparation method of the hard carbon microsphere cathode material of a kind of lithium rechargeable battery |
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| GB853828A (en) * | 1958-07-21 | 1960-11-09 | Staley Mfg Co A E | Methods for treating starch |
| CN103663450B (en) * | 2013-12-19 | 2016-03-16 | 中国科学院过程工程研究所 | A kind of high-specific surface area carbosphere and preparation method thereof |
| CN103647082B (en) * | 2013-12-24 | 2016-05-04 | 中国船舶重工集团公司第七一二研究所 | The preparation method of the hard carbon microsphere cathode material of a kind of lithium rechargeable battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2618729A (en) * | 2022-03-15 | 2023-11-15 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method of hard carbon anode material and use thereof |
| ES2995807R1 (en) * | 2022-03-15 | 2025-11-11 | Guangdong Brunp Recycling Technology Co Ltd | Method of preparing and using hard carbon anode material |
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