CN109911878A - Modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix and preparation method thereof - Google Patents
Modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of lithium ion battery negative, modified hard carbon cathode material of specifically a kind of high capacity pitch/epoxy resin-matrix and preparation method thereof, including being prepared using the following raw material: carbon source precursor material is mixed by pitch and epoxy resin mass ratio by 1:0.2-5；Acid medium, for making catalyst in crosslinked at low temperature polymerization reaction；The acid medium is sulfonic acid or sulfonic acid or the concentrated sulfuric acid；Crosslinking agent is used for crosslinked at low temperature polymerization reaction；Modifying agent is used for crosslinked at low temperature polymerization reaction；The modifying agent uses phosphoric acid and/or boric acid.The present invention is compared with the existing technology, with following technical advantage: using the mixture of pitch and epoxy resin for raw material, hard carbon internal structure is changed after modified dose of doping, effectively increases the efficiency for charge-discharge and cycle performance of hard carbon cathode material, the negative electrode material being prepared is had excellent performance.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, specifically a kind of high capacity pitch/asphalt mixtures modified by epoxy resin
Modified hard carbon cathode material of aliphatic radical and preparation method thereof.
Background technique
Lithium ion battery has high monomer voltage, circulation and the high and good power output of long service life, energy density
The advantages that performance.Currently, the fast development in the fields such as new-energy automobile, large-scale energy-accumulating power station, electric tool is to lithium ion battery
Comprehensive performance more stringent requirements are proposed.How to keep good capacity characteristic and circulation steady under the conditions of high rate charge-discharge
Qualitative difficult point and hot spot as lithium ion battery negative material exploitation.
Conventional graphite class negative electrode material has many advantages, such as that electrode potential is low, has extended cycle life, irreversible capacity is small, becomes mesh
The main negative electrode material of preceding commercial Li-ion battery.But it is poor with the compatibility of electrolyte due to the layer structure of graphite,
The total insertion of lyate ion easily occurs in charge and discharge process and structure is caused to be destroyed, influences the stable circulation of graphite cathode material
Property and coulombic efficiency, are especially reduction of the high rate performance of graphite cathode, are not able to satisfy required by large-sized power battery and continue
Large current discharging capability.
With graphite-phase ratio, hard carbon has isotropic structure feature, and microstructure is in amorphous state, and interlamellar spacing is larger, has
Help the quick diffusion of lithium ion, meanwhile, hard carbon material also has excellent cycle performance, high rate performance and safety, makes it
It attracts attention again in terms of power-type lithium ion battery.
The Nomenclature Composition and Structure of Complexes of hard carbon cathode has important influence to its chemical property.China Patent Publication No. is
CN105293467A disclose it is a kind of prepared using phenolic resin, coal tar pitch and phosphoric acid as raw material through dissolution, solidification and ball milling it is compound
Modified hard carbon cathode material, there is preparation process poor controllability, high production cost to be difficult to realize commercialized lack for this method
It falls into.It is raw material through mixing, pyrolysis and cladding that publication number CN102881869A, which discloses one kind using resin, crystalline flake graphite and boron phosphate,
Processing prepares modified hard carbon cathode material, but it equally exists low yield, and preparation process is cumbersome to be difficult to realize industrialized production
The problems such as.Develop it is novel can yield production type high capacity hard carbon cathode material become this field urgent problem.
Summary of the invention
The purpose of the present invention is overcome in the prior art hard carbon cathode material preparation method it is complicated, it is at high cost, be difficult to advise greatly
The defect of mould industrialized production fills up blank in the prior art to improve the chemical property of hard carbon cathode.
To achieve the above object, a kind of modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix is designed, feature exists
In, including the following raw material is used to be prepared:
Carbon source precursor material is mixed by pitch and epoxy resin mass ratio by 1:0.2-5；
Acid medium, for making catalyst in crosslinked at low temperature polymerization reaction；The carbon source precursor material: acid medium
Mass ratio be 100:1~100:20；The acid medium is sulfonic acid or sulfonic acid or the concentrated sulfuric acid；
Crosslinking agent is used for crosslinked at low temperature polymerization reaction；The carbon source precursor material: the mass ratio of crosslinking agent is 100:
1~100:80；The crosslinking agent be metaformaldehyde, terephthalaldehyde, benzaldehyde, benzyl alcohol, terephthalyl alcohol, furfural, formaldehyde,
1 kind in hexa, hexamethylene diamine, m-phenylene diamine (MPD), m-xylene diamine, ethylenediamine, polyamide or phthalic anhydride or
It is at least two kinds of；
Modifying agent is used for crosslinked at low temperature polymerization reaction；The carbon source precursor material: the mass ratio of modifying agent is 100:
1~100:50；The modifying agent uses phosphoric acid and/or boric acid.
The pitch is using a kind or 2 kinds of mixture in coal asphalt or petroleum asphalt, it is preferred to use softening point 50-
1 kind or 2 kinds of mixture in 150 DEG C of asphalt and purification coal tar pitch.
The epoxy resin uses bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin or phenol
1 kind in formaldehyde epoxy resin or any 2 kinds of mixture.
The sulfonic acid is methanesulfonic acid, p-methyl benzenesulfonic acid, a kind or at least two kinds of in naphthalene sulfonic acids, it is preferred to use right
Toluenesulfonic acid.
The preparation method of the modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix, which is characterized in that including using such as
Lower processing step:
(1), it prepares carbon source presoma: the raw material of the carbon source presoma and acid medium is mixed in a kettle, and
It is melted 0.5~2 hour while stirring with 80~200 DEG C under inert gas protection, the carbon source forerunner of acid medium must be mixed with
Body；
(2), crosslinked at low temperature polymerization reaction: the crosslinking agent is added in the carbon source presoma for being mixed with acid medium and changes
Property agent, and under inert gas protection, it is carried out crosslinked at low temperature polymerization reaction 1~10 hour, is handed over when stirring with 80~200 DEG C
Linked polymer；
(3), hot setting is handled: the cross-linked polymer is under inert gas protection, high with 200~450 DEG C of progress
Then warm curing process 2~8 hours is down to room temperature and is crushed and screened, obtains powder；
(4), pre- carbonization treatment: gained powder under inert gas protection, with 600~800 DEG C carry out pre- carbonization treatment 1~
It 3 hours, is then down to room temperature and is crushed and screened, obtain pre- carbonization powder；
(5), carbonization treatment: it is pre- to be carbonized powder under inert gas protection, with 750~1300 DEG C of progress carbonization treatments 1~6
Hour, carbonization treatment preferably uses 2-4 hours, is down to room temperature, is sieved up to high capacity pitch/epoxy resin-matrix hard carbon cathode
Material；High capacity pitch/epoxy resin-matrix the hard carbon cathode material is the irregular blocky fine particle of surface compact, granularity
Range is 0.2~50 μm, and real density is 1.5~2.2g/cm3, tap density is 0.5~1.2g/cm3, specific surface area be 1~
50m2/g。
Mixing speed when mixing in the preparation carbon source presoma is 500~1000r/min.
Crushing in the hot setting processing is one or more of ball milling, mechanical crushing, air-flow crushing mode；
Crushing in the pre- carbonization treatment is the broken or ball milling that is milled using airflow milling crushing, the mechanical broken, fluidized bed that is milled
It handles, the crushing in pre- carbonization treatment particularly preferably uses fluidized bed to grind pulverization process.
Screening in the hot setting processing was 60~800 the polished standard screen nets；
The volume average particle size of the pre- carbonization powder is 0.2~80 μm.
The carburizing temperature of the carbonization treatment is 900~1200 DEG C.
The pre- carbonization treatment carries out in shaft furnace；
The charing process carries out in atmosphere furnace, batch-type furnace or shaft furnace, it is preferred to use atmosphere furnace.
The present invention compared with the existing technology, has following technical advantage:
It uses the mixture of pitch and epoxy resin for raw material, changes hard carbon internal structure after modified dose of doping, have
Effect improves the efficiency for charge-discharge and cycle performance of hard carbon cathode material, and the negative electrode material being prepared is had excellent performance；
Meanwhile hard carbon yield, the hard carbon of preparation are remarkably improved by the way of cross-linking polymerization again cured reaction
Negative electrode material has reversible capacity height, excellent cycle performance and high rate performance；And gained hard carbon cathode is compatible with PC electrolyte
Property it is good, improve the resistance to low temperature of lithium ion battery, it is long to can satisfy power battery high capacity, fast charging and discharging, service life
It is required that being with a wide range of applications；
Preparation method is simple, and raw material is easy to get extensively, and mild condition is controllable, and prepared hard carbon cathode material has good
Pattern and aperture structure, it is suitable for industrialized production that tap density is big, and industrial production degree and continuous production degree are high.
Detailed description of the invention
Fig. 1 is the Electronic Speculum of the modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix prepared in the embodiment of the present invention 1
Figure.
Specific embodiment
The present invention is further described now in conjunction with accompanying drawings and embodiments.
Heretofore described room temperature is 0~80 DEG C；
The heating rate of heretofore described pre- carbonization treatment is preferably 0.5~20 DEG C/min；The heating speed of carbonization treatment
Rate is preferably 0.5~20 DEG C/min.
Heretofore described inert gas is a kind or at least two kinds of in nitrogen, helium and argon gas.
Embodiment 1
1,1500g coal tar pitch, 1500g novolac epoxy resin and 150g p-methyl benzenesulfonic acid is refined to feed intake in reaction kettle,
Being warming up to 150 DEG C under nitrogen atmosphere makes material melts and is stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction；And gained is produced
Object crosses 150 meshes after being mechanically pulverized, and obtains powder；
4, powder is fitted into shaft furnace, and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, is cooled to
Room temperature discharging, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so, obtain pre- carbonization powder；
5, pre- carbonization powder being reloaded into atmosphere furnace, 2 DEG C/min is warming up to 1100 DEG C of carbonization 2h under nitrogen protection,
Room temperature is cooled to discharge up to modified hard carbon cathode material, referring to Fig. 1.
Embodiment 2
1,1500g coal tar pitch, 1500g novolac epoxy resin and 150g p-methyl benzenesulfonic acid is refined to feed intake in reaction kettle,
Being warming up to 150 DEG C under nitrogen atmosphere makes material melts and is stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes are crossed after mechanical crushing, obtain powder；
4, powder is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room
Temperature discharging, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so, obtain pre- carbonization powder；
5, pre- carbonization powder being reloaded into atmosphere furnace, 2 DEG C/min is warming up to 1100 DEG C of carbonization 2h under nitrogen protection,
Room temperature is cooled to discharge up to modified hard carbon cathode material.
Embodiment 3
1,1500g coal tar pitch, 1500g novolac epoxy resin and 150g p-methyl benzenesulfonic acid is refined to feed intake in reaction kettle,
Being warming up to 150 DEG C under nitrogen atmosphere makes material melts and is stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes are crossed after mechanical crushing, obtain powder；
4, powder is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room
Temperature discharging, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so, obtain pre- carbonization powder；
5, pre- carbonization powder being reloaded into atmosphere furnace, 2 DEG C/min is warming up to 1000 DEG C of carbonization 2h under nitrogen protection,
Room temperature is cooled to discharge up to modified hard carbon cathode material.
Embodiment 4
1,1500g coal tar pitch, 1500g novolac epoxy resin and 150g p-methyl benzenesulfonic acid is refined to feed intake in reaction kettle,
Being warming up to 150 DEG C under nitrogen atmosphere makes material melts and is stirred 1h；
2, the phosphoric acid solution that 300g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes are crossed after mechanical crushing, obtain powder；
4, powder is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room
Temperature discharging, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so, obtain pre- carbonization powder；
5, pre- carbonization powder is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1100 DEG C of 2 h of carbonization, dropped
It warms to room temperature and discharges up to modified hard carbon cathode material.
Embodiment 5
1,2000g coal tar pitch, 1000g novolac epoxy resin and 150g p-methyl benzenesulfonic acid is refined to feed intake in reaction kettle,
Being warming up to 150 DEG C under nitrogen atmosphere makes material melts and is stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes are crossed after mechanical crushing, obtain powder；
4, powder is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room
Temperature discharging, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so, obtain pre- carbonization powder；
5, pre- carbonization powder being reloaded into atmosphere furnace, 2 DEG C/min is warming up to 1100 DEG C of carbonization 2h under nitrogen protection,
Room temperature is cooled to discharge up to modified hard carbon cathode material.
Embodiment 6
1,1000g coal tar pitch, 2000g novolac epoxy resin and 150g p-methyl benzenesulfonic acid is refined to feed intake in reaction kettle,
Being warming up to 150 DEG C under nitrogen atmosphere makes material melts and is stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes are crossed after mechanical crushing, obtain powder；
4, powder is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room
Temperature discharging, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so, obtain pre- carbonization powder；
5, pre- carbonization powder being reloaded into atmosphere furnace, 2 DEG C/min is warming up to 1100 DEG C of carbonization 2h under nitrogen protection,
Room temperature is cooled to discharge up to modified hard carbon cathode material.
Comparative example 1
1,3000g is refined into coal tar pitch and 150g p-methyl benzenesulfonic acid feeds intake in reaction kettle, be warming up under nitrogen atmosphere
150 DEG C make material melts and are stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes, extracting screen underflow are crossed after mechanical crushing；
4, it is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room temperature and go out
Material, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1100 DEG C of carbonization 2h, be cooled to room temperature discharging
Up to modified hard carbon cathode material.
Comparative example 2
1,3000g novolac epoxy resin and 150g p-methyl benzenesulfonic acid are fed intake in reaction kettle, is heated up under nitrogen atmosphere
Make material melts to 150 DEG C and is stirred 1h；
2, the phosphoric acid solution that 600g furfural and 300g mass fraction are 85% is added and under nitrogen atmosphere and stirring condition
It is warming up to 180 DEG C of progress cross-linking polymerization 2h；
3, temperature is increased again to 450 DEG C of progress curing reaction 6h；It is cooled to room temperature discharging after reaction.By products therefrom
150 meshes, extracting screen underflow are crossed after mechanical crushing；
4, it is fitted into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room temperature and go out
Material, is handled using air-flow crushing and adjusts D50 partial size to 9 μm or so；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1100 DEG C of carbonization 2h, be cooled to room temperature discharging
Up to modified hard carbon cathode material.
Partial size, very close is carried out respectively to the modification hard carbon cathode material in Examples 1 to 6 and comparative example 1~2
The test of degree, tap density and specific surface area, is as a result listed in table 1.Instrument title used in testing and model are as follows: partial size: horse
You are literary laser particle size analyzer MS2000；Real density: the full-automatic real density analyzer of U.S.'s health tower UltraPYC 1200e type；
Tap density: tap density tester FZS4-4B；Specific surface area: health tower specific surface area measuring instrument NOVA2000e.
Table 1
The modification hard carbon cathode material in Examples 1 to 6 and comparative example 1~2 is carried out using half-cell test method
Charge-discharge property, cycle performance test and high rate performance test, are as a result listed in table 1.The test method of half-cell are as follows: with N-
Methyl pyrrolidone is the Kynoar solution that solvent prepares that mass fraction is 6~7%, by modified hard carbon cathode material, is gathered
Vinylidene, conductive carbon black 90:5:5 in mass ratio are uniformly mixed, and are applied on copper foil, and it is 110 that the pole piece coated, which is put into temperature,
Be dried in vacuo in DEG C vacuum oven 4 hours it is spare.Then 2430 are assembled into that glove box of the German meter Kai Luo of applying argon gas
Type button cell is by EC:DMC:EMC=1:1:1 (volume ratio) mixed liquor with the three component mixed solvents of 1mol/L LiPF6
Electrolyte, metal lithium sheet are to carry out electrochemistry to the half-cell of assembling on U.S.'s Arbin electrochemical detection system to electrode
Can test, charging/discharging voltage range is 0mV to 2.0V, and test multiplying power is 0.1C, 1C and 10C, test reversible capacity, for the first time for the first time
Coulombic efficiency and cycle performance.The discharge capacity of coulombic efficiency=initial charge capacity/for the first time for the first time.
As shown in Table 1, using purification coal tar pitch and novolac epoxy resin it is composite modified after, embodiment 1, embodiment 2 and real
The modification hard carbon cathode material of electrochemical performance can be obtained by applying example 5.
Reversible capacity is 360mAh/g to the resulting modified hard carbon cathode of embodiment 1 for the first time at 0.1C, for the first time coulombic efficiency
Capacity retention ratio is 95.2% after being 96.5%, 1C charge and discharge cycles 100 times for 83.2%, 10C/1C capacity retention ratio.
Reversible capacity is 377mAh/g to the resulting modified hard carbon cathode of embodiment 2 for the first time at 0.1C, for the first time coulombic efficiency
Capacity retention ratio is 96.7% after being 97.3%, 1C charge and discharge cycles 100 times for 84.8%, 10C/1C capacity retention ratio.
Reversible capacity is 385mAh/g to the resulting modified hard carbon cathode of embodiment 5 for the first time at 0.1C, for the first time coulombic efficiency
Capacity retention ratio is 95.1% after being 96.5%, 1C charge and discharge cycles 100 times for 85.5%, 10C/1C capacity retention ratio.
In comparison, the reversible capacity of comparative example 1 and comparative example 2 and coulombic efficiency is substantially reduced for the first time,
The compound fault of construction for helping to improve one-component carbon source for showing coal tar pitch and novolac epoxy resin, is conducive to improve gained
Reversible capacity, coulombic efficiency, multiplying power and the cycle performance of hard carbon material.Compared with the traditional graphite negative electrode, modification of the invention is hard
Carbon negative pole material has higher capacity and high rate charge-discharge performance, is suitably applied cathode material of lithium-ion power battery.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
Claims (10)
1. a kind of modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix, which is characterized in that including using the following raw material system
It is standby to form:
Carbon source precursor material is mixed by pitch and epoxy resin mass ratio by 1:0.2-5；
Acid medium, for making catalyst in crosslinked at low temperature polymerization reaction；The carbon source precursor material: the matter of acid medium
Amount is than being 100:1~100:20；The acid medium is sulfonic acid or sulfonic acid or the concentrated sulfuric acid；
Crosslinking agent is used for crosslinked at low temperature polymerization reaction；The carbon source precursor material: the mass ratio of crosslinking agent be 100:1~
100:80；The crosslinking agent is metaformaldehyde, terephthalaldehyde, benzaldehyde, benzyl alcohol, terephthalyl alcohol, furfural, formaldehyde, six
1 kind in methenamine, hexamethylene diamine, m-phenylene diamine (MPD), m-xylene diamine, ethylenediamine, polyamide or phthalic anhydride or extremely
It is 2 kinds few；
Modifying agent is used for crosslinked at low temperature polymerization reaction；The carbon source precursor material: the mass ratio of modifying agent be 100:1~
100:50；The modifying agent uses phosphoric acid and/or boric acid.
2. the modified hard carbon cathode material of high capacity pitch as described in claim 1/epoxy resin-matrix, it is characterised in that: described
Pitch is using a kind or 2 kinds of mixture in coal asphalt or petroleum asphalt.
3. the modified hard carbon cathode material of high capacity pitch as described in claim 1/epoxy resin-matrix, it is characterised in that: described
Epoxy resin using in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin or novolac epoxy resin
1 kind or any 2 kinds of mixture.
4. the modified hard carbon cathode material of high capacity pitch as described in claim 1/epoxy resin-matrix, it is characterised in that: described
Sulfonic acid be methanesulfonic acid, p-methyl benzenesulfonic acid, a kind or at least two kinds of in naphthalene sulfonic acids.
5. the preparation side of the modified hard carbon cathode material of high capacity pitch/epoxy resin-matrix as described in any one of Claims 1 to 4
Method, which is characterized in that including using following processing step:
(1), it prepares carbon source presoma: the raw material of the carbon source presoma and acid medium being mixed in a kettle, and lazy
Property gas shield under with 80~200 DEG C while stirring melt 0.5~2 hour, the carbon source presoma of acid medium must be mixed with；
(2), the crosslinking agent and modification crosslinked at low temperature polymerization reaction: are added in the carbon source presoma for being mixed with acid medium
Agent, and under inert gas protection, it is carried out crosslinked at low temperature polymerization reaction 1~10 hour, is crosslinked when stirring with 80~200 DEG C
Polymer；
(3), hot setting is handled: the cross-linked polymer is under inert gas protection, solid with 200~450 DEG C of progress high temperature
Change processing 2~8 hours, is then down to room temperature and is crushed and screened, obtain powder；
(4), pre- carbonization treatment: it is small that gained powder carries out pre- carbonization treatment 1~3 under inert gas protection, with 600~800 DEG C
When, it is then down to room temperature and is crushed and screened, obtain pre- carbonization powder；
(5), carbonization treatment: pre- carbonization powder is under inert gas protection, small with 750~1300 DEG C of progress carbonization treatments 1~6
When, it is down to room temperature, is sieved up to high capacity pitch/epoxy resin-matrix hard carbon cathode material；High capacity pitch/the epoxy resin
Base hard carbon cathode material is the irregular blocky fine particle of surface compact, and particle size range is 0.2~50 μm, real density 1.5
~2.2g/cm3, tap density is 0.5~1.2g/cm3, specific surface area is 1~50m2/g。
6. the preparation method of the modified hard carbon cathode material of high capacity pitch as claimed in claim 5/epoxy resin-matrix, feature exist
In: mixing speed when mixing in the preparation carbon source presoma is 500~1000r/min.
7. the preparation method of the modified hard carbon cathode material of high capacity pitch as claimed in claim 5/epoxy resin-matrix, feature exist
In:
Crushing in the hot setting processing is one or more of ball milling, mechanical crushing, air-flow crushing mode；
Crushing in the pre- carbonization treatment is the broken or ball-milling treatment that is milled using airflow milling crushing, the mechanical broken, fluidized bed that is milled.
8. the preparation method of the modified hard carbon cathode material of high capacity pitch as claimed in claim 5/epoxy resin-matrix, feature exist
In:
Screening in the hot setting processing was 60~800 the polished standard screen nets；
The volume average particle size of the pre- carbonization powder is 0.2~80 μm.
9. the preparation method of the modified hard carbon cathode material of high capacity pitch as claimed in claim 5/epoxy resin-matrix, feature exist
In: the carburizing temperature of the carbonization treatment is 900~1200 DEG C.
10. the preparation method of the modified hard carbon cathode material of high capacity pitch as claimed in claim 5/epoxy resin-matrix, feature
It is:
The pre- carbonization treatment carries out in shaft furnace；
The charing process carries out in atmosphere furnace, batch-type furnace or shaft furnace.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551505A (en) * | 2020-12-11 | 2021-03-26 | 广东凯金新能源科技股份有限公司 | Preparation method of hard carbon-based negative electrode material |
| CN113415799A (en) * | 2021-06-30 | 2021-09-21 | 北京化工大学 | PTCDA modified resin-based carbon material and preparation method and application thereof |
| CN113880068A (en) * | 2021-09-29 | 2022-01-04 | 蜂巢能源科技有限公司 | Hard carbon composite material and preparation method and application thereof |
| CN114709408A (en) * | 2022-04-18 | 2022-07-05 | 鸡西市唯大新材料科技有限公司 | Preparation method of sodium ion hard carbon negative electrode material |
| CN115259134A (en) * | 2022-08-30 | 2022-11-01 | 山东零壹肆先进材料有限公司 | Hard carbon negative electrode material prepared by asphalt-based crosslinking method, and preparation method and application thereof |
| CN115806284A (en) * | 2022-10-21 | 2023-03-17 | 中科(宜兴)新材料研究有限公司 | Preparation method for improving yield of biomass-based hard carbon |
| CN116812913A (en) * | 2023-08-30 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7368009B2 (en) * | 2004-06-25 | 2008-05-06 | Fuji Xerox Co., Ltd. | Carbon fine particle structure and process for producing the same, carbon fine particle transcriptional body for producing the same, solution for producing carbon fine particle structure, carbon fine particle structure, electronic device using carbon fine particle structure and process for producing the same, and integrated circuit |
| CN102479942A (en) * | 2010-11-30 | 2012-05-30 | 上海杉杉科技有限公司 | Hard carbon negative electrode material, its preparation method and application |
| CN102723492A (en) * | 2012-06-28 | 2012-10-10 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing hard carbon material and lithium ion battery |
| CN103754858A (en) * | 2014-01-10 | 2014-04-30 | 纪效波 | Hard carbon cathode material for power energy storage battery and preparation method thereof |
| CN105293467A (en) * | 2015-10-21 | 2016-02-03 | 山东玉皇新能源科技有限公司 | Phenolic resin/coal tar pitch composite-base modified hard carbon negative electrode material and preparation method and application thereof |
| CN106532009A (en) * | 2016-12-21 | 2017-03-22 | 上海杉杉科技有限公司 | Preparation method of high capacity lithium ion battery hard carbon composite negative electrode material |
| CN106995210A (en) * | 2017-04-21 | 2017-08-01 | 上海杉杉科技有限公司 | A kind of preparation method of the spherical hard charcoal negative material of high-capacity lithium ion cell |
-
2017
- 2017-12-13 CN CN201711326234.5A patent/CN109911878A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7368009B2 (en) * | 2004-06-25 | 2008-05-06 | Fuji Xerox Co., Ltd. | Carbon fine particle structure and process for producing the same, carbon fine particle transcriptional body for producing the same, solution for producing carbon fine particle structure, carbon fine particle structure, electronic device using carbon fine particle structure and process for producing the same, and integrated circuit |
| CN102479942A (en) * | 2010-11-30 | 2012-05-30 | 上海杉杉科技有限公司 | Hard carbon negative electrode material, its preparation method and application |
| CN102723492A (en) * | 2012-06-28 | 2012-10-10 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing hard carbon material and lithium ion battery |
| CN103754858A (en) * | 2014-01-10 | 2014-04-30 | 纪效波 | Hard carbon cathode material for power energy storage battery and preparation method thereof |
| CN105293467A (en) * | 2015-10-21 | 2016-02-03 | 山东玉皇新能源科技有限公司 | Phenolic resin/coal tar pitch composite-base modified hard carbon negative electrode material and preparation method and application thereof |
| CN106532009A (en) * | 2016-12-21 | 2017-03-22 | 上海杉杉科技有限公司 | Preparation method of high capacity lithium ion battery hard carbon composite negative electrode material |
| CN106995210A (en) * | 2017-04-21 | 2017-08-01 | 上海杉杉科技有限公司 | A kind of preparation method of the spherical hard charcoal negative material of high-capacity lithium ion cell |
Non-Patent Citations (6)
| Title |
|---|
| 《化工百科全书》编辑委员会: "《化工百科全书 第4卷 发光材料-氟 fa-fu》", 30 September 1993, 化学工业出版社 * |
| 李国欣: "《新型化学电源技术概论》", 31 May 2007, 上海科学技术出版社 * |
| 李青山 等: "《微型高分子化学实验》", 31 August 2003, 化学工业出版社 * |
| 童凤昭: "《工程材料》", 28 February 1987, 上海交通大学出版社 * |
| 蒋文忠: "《炭石墨制品及其应用》", 31 March 2017, 冶金工业出版社 * |
| 谢凯 等: "《新一代锂二次电池技术》", 31 August 2013, 国防工业出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551505A (en) * | 2020-12-11 | 2021-03-26 | 广东凯金新能源科技股份有限公司 | Preparation method of hard carbon-based negative electrode material |
| WO2022121141A1 (en) * | 2020-12-11 | 2022-06-16 | 广东凯金新能源科技股份有限公司 | Method for preparing hard carbon-based negative electrode material |
| CN113415799A (en) * | 2021-06-30 | 2021-09-21 | 北京化工大学 | PTCDA modified resin-based carbon material and preparation method and application thereof |
| CN113880068A (en) * | 2021-09-29 | 2022-01-04 | 蜂巢能源科技有限公司 | Hard carbon composite material and preparation method and application thereof |
| CN114709408A (en) * | 2022-04-18 | 2022-07-05 | 鸡西市唯大新材料科技有限公司 | Preparation method of sodium ion hard carbon negative electrode material |
| CN115259134A (en) * | 2022-08-30 | 2022-11-01 | 山东零壹肆先进材料有限公司 | Hard carbon negative electrode material prepared by asphalt-based crosslinking method, and preparation method and application thereof |
| CN115806284A (en) * | 2022-10-21 | 2023-03-17 | 中科(宜兴)新材料研究有限公司 | Preparation method for improving yield of biomass-based hard carbon |
| CN116812913A (en) * | 2023-08-30 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
| CN116812913B (en) * | 2023-08-30 | 2023-11-21 | 乌海宝杰新能源材料有限公司 | High-reversible-capacity hard carbon negative electrode material and preparation method thereof |
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