CN107993853B - A kind of negative electrode material that soft or hard carbon is compound, preparation method and the capacitor comprising the negative electrode material - Google Patents
A kind of negative electrode material that soft or hard carbon is compound, preparation method and the capacitor comprising the negative electrode material Download PDFInfo
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- CN107993853B CN107993853B CN201711240094.XA CN201711240094A CN107993853B CN 107993853 B CN107993853 B CN 107993853B CN 201711240094 A CN201711240094 A CN 201711240094A CN 107993853 B CN107993853 B CN 107993853B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of soft carbon and the compound negative electrode material of hard carbon, preparation method and the capacitor comprising the negative electrode material.The preparation method of the negative electrode material includes: 1) to heat soft carbon presoma and hard carbon presoma, carries out melting mixing, obtains mixture；2) mixture that step 1) obtains is granulated, obtains cathode presoma；3) carbonization treatment is carried out to cathode presoma described in step 2), obtains the negative electrode material.The negative electrode material is the composite negative pole material comprising soft carbon and hard carbon, and wherein soft carbon and hard carbon mutually mix, dispersed distribution.The present invention also provides the capacitors comprising the negative electrode material.The preparation method process is simple, high yield rate, consistency are good；The negative electrode material is at low cost, and performance is high, has been obtained by the combination of soft carbon and hard carbon compared with high charge-discharge efficiencies and low internal resistance.
Description
Technical field
The invention belongs to electrochemical energy storage component fields, and in particular to a kind of negative electrode material that soft or hard carbon is compound, system
Preparation Method and capacitor comprising the negative electrode material.
Background technique
The lithium-ion capacitor new energy energy storage component emerging as one kind, relatively traditional double layer capacitor, both
The characteristics of maintaining the supercapacitor high power long-life, while there has also been larger relative to double layer capacitor for its energy density
The raising of degree.
The negative electrode material of lithium-ion capacitor has quick intercalation/deintercalation lithium as the negative electrode material of lithium ion battery
The ability of ion.In order to play the capacity of positive double layer electrodes as far as possible, lithium-ion capacitor negative electrode material is usually required
In 0.3~0V vs.Li+The intercalation/deintercalation of lithium ion is carried out in/Li potential range.It is compared with lithium ion battery, lithium-ion electric
Containers demand negative electrode material has extra long life and high temperature durability, super large rate charge-discharge ability, high charging and discharging capacity
Etc. characteristics so that high performance amorphous Carbon anode become lithium-ion capacitor negative electrode material optimal selection.
Common amorphous carbons negative electrode material has soft carbon and hard carbon two major classes type.Soft carbon is graphitizable carbon, can under high temperature
It is converted to graphite-structure；Hard carbon is non-graphitized carbon, cannot be converted to graphite-structure under high temperature.According to Carbon 39
(2001), the amorphous carbon removal lithium embedded mechanism of 399-410 document, the embedding lithium of amorphous carbon are mainly made of 5 parts: (I) electric charge transfer
Micropore (V) hetero atom between " cluster " gap (IV) graphite flake layer at insertion (III) the graphite flake layer edge of (II) class graphite flake layer
The defect of generation.Wherein, soft carbon storage lithium is mainly (I) (II) (III) part, and hard carbon is then (I)-(V) part.To lithium-ion electric
For container, the minority (II) of (IV) part/soft carbon of hard carbon is partially the main voltage belt of amorphous carbon negative pole material charge and discharge
Between.
CN200680038604 proposes a kind of cathode using polyacene class hard carbon (PAS) as lithium-ion capacitor at first
Material, the negative electrode material is in 0.15~0V vs.Li+There is good chemical property within the scope of/Li.External producer is special herein
On the basis of benefit, take the lead in developing the lithium-ion capacitor using polyacene class amorphous carbon (PAS) as negative electrode material.
CN201380044862, which is proposed, a kind of prepares lithium-ion capacitor hard carbon cathode material using plant raw material
The method of material.In order to improve intercalation/deintercalation ability of the lithium ion in negative electrode material, the preferably specific surface of amorphous carbon negative pole material
Product is in 40~130m2/g。
It is wanted to meet lithium-ion capacitor within the scope of 0.3~0V vs.Li+/Li with big charging and discharging capacity
It asks, CN200680038604 and CN201380044862 are in the capacity for improving hard carbon (IV) part as far as possible.But it is high
(IV) capacity means more microcellular structures inside hard carbon material, this also leads to the internal resistance of hard carbon material and lithium-ion capacitor
Increase/efficiency for charge-discharge reduces, and there are the risks of hard carbon " voltage delay " and analysis lithium.
WO2015157324A3 proposes a kind of mix hard carbon material and soft carbon material and is used as lithium-ion capacitor cathode
The scheme of material.By mixing soft carbon material in hard carbon material, compares and use pure hard carbon cathode material, lithium-ion capacitor table
Reveal better chemical property.However the patent does not provide the method for preparing this negative electrode material from initial feed, simultaneously
The product chemical property that the patent obtains needs to be further increased.
Therefore, the manufacturing method for developing a kind of excellent soft or hard carbon compound cathode materials has important show for this field
Sincere justice and industrial value.
Summary of the invention
To solve the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of compound negative of soft or hard carbon
Pole material, preparation method and the capacitor comprising the negative electrode material.In the present invention, the compound negative electrode material of the soft or hard carbon
Refer to the composite negative pole material comprising soft carbon and hard carbon.Preparation method provided by the invention is granulated and is carbonized by melting mixing
Etc. series of steps prepared the compound negative electrode material of soft or hard carbon, this method is at low cost, and process is simple, high yield rate.The present invention
The compound negative electrode material efficiency for charge-discharge of the soft or hard carbon provided is high, and internal resistance is low, is had using the capacitor of the negative electrode material good
Performance.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of negative electrode material, the described method comprises the following steps:
(1) soft carbon presoma and hard carbon presoma are heated, carries out melting mixing, obtains mixture；
(2) mixture obtained to step (1) is granulated, and obtains cathode presoma；
(3) carbonization treatment is carried out to step (2) the cathode presoma, obtains the negative electrode material.
In preparation method provided by the invention, keep it completely molten by carrying out heating to soft carbon presoma and hard carbon presoma
Melt, soft carbon presoma and hard carbon presoma can be mixed extremely uniform by this, by subsequent granulation and carbonization treatment, soft carbon
Presoma and hard carbon presoma are separately converted to soft carbon and hard carbon, it will be able to obtain soft carbon and hard carbon is homogenously mixed together to be formed
Soft or hard carbon compound cathode materials.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As the present invention preferably technical solution, in step (1), the temperature of the heating is 180 DEG C~230 DEG C, such as
180 DEG C, 200 DEG C, 210 DEG C, 220 DEG C or 230 DEG C etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable.This temperature range can not only guarantee completely to melt soft carbon presoma and hard carbon presoma, but also
Not will cause soft carbon presoma and hard carbon presoma be carbonized in advance reduce final products quality.
Preferably, in step (1), the melting mixing carries out in a kettle.According to circumstances, pyroreaction can be used
Kettle carries out melting mixing.
Preferably, the melting mixing is also with stirring.
Preferably, the time of the melting mixing is 5h~8h, such as 5h, 6h, 7h or 8h etc., it is not limited to listed
The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable.
As currently preferred technical solution, in step (1), the soft carbon presoma include selected from coal tar pitch and petroleum asphalt,
In petroleum coke, needle coke, carbonaceous mesophase spherules or carbon fiber any one or at least two combination, it is typical but unrestricted
The combination of property has: the combination of the combination of coal tar pitch and asphalt, petroleum coke and needle coke, carbonaceous mesophase spherules and carbon fiber
Combination, asphalt, petroleum coke and combination of needle coke etc., preferably coal tar pitch.
Preferably, the coal tar pitch is isotropic pitch.
Preferably, the softening point of the coal tar pitch is 75 DEG C~95 DEG C.
Preferably, the degree of graphitization of the coal tar pitch is 50%~80%, such as 50%, 60%, 70% or 80% etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in step (1), the hard carbon presoma includes sucrose, phenolic resin, epoxy resin, poly furfuryl alcohol, smokeless
In coal, rice husk, glucose, polyvinyl chloride or cellulose any one or at least two combination, it is typical but be non-limited
Combination have: the combination of the combination of the combination of sucrose and phenolic resin, epoxy resin and poly furfuryl alcohol, anthracite and rice husk, grape
Sugar, polyvinyl chloride and combination of cellulose etc., preferably sucrose.
Preferably, the fusing point of the sucrose is 160 DEG C~180 DEG C.
Preferably, purity >=99.7% of the sucrose.
Preferably, in step (1), the mass ratio of the soft carbon presoma and hard carbon presoma is 5:95~95:5, such as
5:95,1:9,2:8,3:7,4:7,5:7,6:7,1:1,7:6,7:5,7:4,7:3,8:2,9:1 or 95:5 etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 3:7~7:3.
As the present invention preferably technical solution, in step (2), the method for the granulation is that atomization is granulated, preferably more
Grade atomization is granulated.It in the present invention, is granulated using atomization, especially multistage atomizing is granulated, the mixture that step (1) can be made to obtain
Little particle is formed, the mixture for effectivelying prevent step (1) to obtain forms bulk, and then prevents in subsequent carbonisation because of carbonization
Degree unevenness causes product quality to decline.
Preferably, in step (2), obtained cathode presoma is spheric granules.
Preferably, in step (2), the D50 of obtained cathode presoma is 10 μm~30 μm, such as 10 μm, 15 μm, 20 μ
M, 25 μm or 30 μm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As the present invention preferably technical solution, in step (3), the carbonization treatment the following steps are included:
Step (2) the cathode presoma is carried out pre- carbonization treatment by (3 ') under an inert atmosphere, obtains pre- char-forming material；
Step (3 ') the pre- char-forming material is carbonized by (3 ") under an inert atmosphere, obtains the negative electrode material.
It is because pre- carbonization can remove step (2) and obtain using the technique being carbonized again that is first carbonized in advance in the present invention
Cathode presoma in water and impurity cathode precursor can be made to be changed into negative electrode material using subsequent carbonisation；Such as
For fruit without being carbonized in advance, the water and impurity that step (2) obtains in cathode presoma can make the product knot obtained after carbonization
Block influences properties of product.
As currently preferred technical solution, in step (3 '), the inert atmosphere is nitrogen atmosphere and/or argon gas gas
Atmosphere, the present invention in, the nitrogen atmosphere and/or argon atmosphere refer to: can be nitrogen atmosphere, or argon atmosphere, and also
It can be the mixed atmosphere of nitrogen and argon gas, preferably nitrogen atmosphere.
Preferably, in step (3 '), the pre- carbonization carries out in carbide furnace.
Preferably, in step (3 '), the temperature of the pre- carbonization is 250 DEG C~450 DEG C, such as 250 DEG C, 280 DEG C, 300
DEG C, 320 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 380 DEG C, 400 DEG C, 420 DEG C or 450 DEG C etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, and preferably 350 DEG C~400 DEG C.
Preferably, in step (3 '), time of the pre- carbonization is 3h~5h, such as 3h, 3.5h, 4h, 4.5h or 5h etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in step (3 "), the inert atmosphere be nitrogen atmosphere and/or argon atmosphere, the present invention in, the nitrogen
Gas atmosphere and/or argon atmosphere refer to: can be nitrogen atmosphere, or argon atmosphere can also be nitrogen and argon gas
Mixed atmosphere, preferably nitrogen atmosphere.
Preferably, in step (3 "), the carbonization carries out in tube furnace.
Preferably, in step (3 "), the temperature of the carbonization is 750 DEG C~1350 DEG C, such as 750 DEG C, 800 DEG C, 850
℃、900℃、950℃、1000℃、1030℃、1060℃、1080℃、1100℃、1150℃、1200℃、1250℃、1300℃
Or 1350 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably
It is 950 DEG C~1150 DEG C.
Preferably, in step (3 "), time of the carbonization is 5h~8h, such as 5h, 6h, 7h or 8h etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
As currently preferred technical solution, the method also includes step (4): step (3) being obtained described negative
Pole material is by crushing, classification obtains purification negative electrode material after handling.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps:
(1) coal tar pitch and sucrose are added in reaction kettle with the ratio of 3:7~7:3, at 180 DEG C~230 DEG C and are stirred
Under the conditions of, melting mixing 5h~8h obtains mixture；The coal tar pitch is isotropic pitch, and softening point is 75 DEG C~95 DEG C,
Degree of graphitization is 50%~80%；The fusing point of the sucrose is 160 DEG C~180 DEG C, purity >=99.7%；
(2) mixture obtained to step (1) carries out atomization granulation, obtains cathode presoma；The cathode presoma is
Spheric granules, D50 are 10 μm~30 μm；
(3 ') by under step (2) the cathode presoma nitrogen atmosphere in carbide furnace with 350 DEG C~400 DEG C pre- carbonization 3h
~5h obtains pre- char-forming material；
Step (3 ') the pre- char-forming material is carbonized in a nitrogen atmosphere in tube furnace with 950 DEG C~1150 DEG C by (3 ")
5h~8h obtains the negative electrode material；
(4) by the negative electrode material that step (3 ") obtains by crushing, purification negative electrode material is obtained after classification processing.
The further preferred technical solution uses commercially available cheap coal tar pitch and sucrose, by mixing in pyroreaction kettle
Two kinds of materials for closing stirring melting, carry out the uniform mixing of material.It is granulated, is obtained spherical by the atomization to fused materials
Cathode presoma.By to the series of processes such as the pre- carbonization of presoma and high temperature cabonization, crushing and classification, being prepared for that there is good electricity
The compound negative electrode material of the soft or hard carbon of chemical property.
Second aspect, the present invention provides a kind of negative electrode material being prepared according to first aspect the method, described negative
Pole material is the composite negative pole material comprising soft carbon and hard carbon, and wherein soft carbon and hard carbon mutually mix, dispersed distribution.
Before negative electrode material provided by the invention makes soft carbon presoma and hard carbon by way of melting during the preparation process
The mixing for driving body reaches the high uniformity, divides soft carbon presoma and hard carbon presoma by subsequent granulation and carbonization treatment
It is not converted into soft carbon and hard carbon, soft carbon and hard carbon mix very uniform in finally obtained negative electrode material product, therefore have
Efficiency for charge-discharge is high, the low advantage of internal resistance.
Preferably, the negative electrode material is lithium-ion capacitor negative electrode material.
The third aspect, the present invention provide a kind of capacitor comprising negative electrode material described in second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) preparation method provided by the invention is by carrying out melting mixing to soft carbon presoma and hard carbon presoma, being granulated
And carbonization treatment, using cheap coal tar pitch and sucrose as raw material, having the advantages that for being prepared is low cost and high performance
Negative electrode material, this method have the advantages that process is simple, high yield rate, consistency are good；
(2) the advantages of soft or hard carbon compound cathode materials provided by the invention have both soft carbon and hard carbon material is improving hard carbon
While (IV) portion capacity, by the combination of soft or hard carbon maintain negative electrode material relatively high charge-discharge efficiencies and low internal resistance,
AC internal Resistance can be down to 8.76m Ω；
(3) capacitor performance provided by the invention comprising negative electrode material described in second aspect is excellent, and condenser capacity can
Up to 1074F, 10000 circulation volume conservation rates are up to 92.6%.
Detailed description of the invention
Fig. 1 is the grain size distribution of the cathode presoma of 1 step of embodiment (2) preparation；
Fig. 2 is the cycle life figure of the lithium-ion capacitor for the negative electrode material production being prepared with embodiment 2；
Fig. 3 is curve graph of the negative electrode material that is prepared of embodiment 3, comparative example 1 and comparative example 2 to lithium charge and discharge.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.But following embodiments are only
Simple example of the invention does not represent or limits the scope of the present invention, and the scope of the present invention is with claim
Subject to book.
Embodiment 1
The present embodiment provides a kind of preparation method of negative electrode material, method particularly includes:
(1) weigh coal tar pitch (Hebei produce, 80 DEG C of softening point, soft carbon presoma) 50kg, sucrose (Jiangsu produce, purity >=
99.8%, 165 DEG C of fusing point, hard carbon presoma) 50kg, pyroreaction kettle is put into according to soft carbon and hard carbon presoma 1:1 mass ratio
In (Jiangsu production), 220 DEG C of high-temperature stirring 7h obtain uniformly mixed presoma fusant.
(2) presoma fusant is handled through multistage atomizing, obtains spherical cathode granular precursor.Spherical precursor particle exists
Testing graininess is carried out on laser particle analyzer (Britain's production).
(3 ') cathode granular precursor, in 360 DEG C of pre- carbonization treatment 4h, removes presoma in the carbide furnace of nitrogen protection
In moisture and volatile impurity.
(3 ") in advance carbonization after presoma under nitrogen protection atmosphere 1050 DEG C of high temperature cabonization 5h in tube furnace, born
Pole material.
(4) negative electrode material obtains the negative electrode material of polishing after crushing and classification is handled.
The negative electrode material of preparation is according to negative electrode material: conductive carbon black: Kynoar (PVDF)=90:3:7 ratio
Slurry is prepared, is coated on the copper foil of 9 μ m thicks and dry roll-in obtains the electrode of 90 μm of overall thickness.Electrode is cut into 41mm*
The size of 27mm with metal lithium sheet is the Soft Roll sample for electrode being made two electrodes, and charge and discharge electrical measurement is carried out within the scope of 0~1.5V
Examination.
Using production with active carbon electrode be anode, embodiment 1 negative electrode material preparation electrode as cathode, pass through electrochemistry
The mode assembling design capacity of pre- lithium is the lithium-ion capacitor sample of 600F, and the charge and discharge tested within the scope of 3.8~2.2V follow
The ring service life.
Fig. 1 is the grain size distribution of the cathode presoma of 1 step of embodiment (2) preparation, can be seen that this implementation by the figure
Cathode presoma prepared by example step (2) has good particle diameter distribution and particle concentration degree, and D50 is at 14.248 μm or so.This
Outside, the diagram data is analyzed, the cathode precursor samples D10 of 1 step of embodiment (2) preparation can be obtained at 7.414 μm or so, D90
At 22.321 μm or so.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Embodiment 2
The present embodiment provides a kind of preparation method of negative electrode material, referring to embodiment 1, difference is specific method, step
Suddenly in (1), by coal tar pitch 70kg and sucrose 30kg according in soft carbon and hard carbon presoma 7:3 mass ratio investment pyroreaction kettle.
Fig. 2 is the cycle life figure of the lithium-ion capacitor for the negative electrode material production being prepared with embodiment 2, by the figure
It can be seen that the 600F lithium-ion capacitor sample for the negative electrode material production being prepared using embodiment 2, in 3.8~2.2V model
With 10A constant current charge-discharge in enclosing, capacity stills remain in 90% or more after 10000 circulations.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Embodiment 3
The present embodiment provides a kind of preparation method of negative electrode material, referring to embodiment 1, difference is specific method, step
Suddenly in (1), by coal tar pitch 30kg and sucrose 70kg according in soft carbon and hard carbon presoma 3:7 mass ratio investment pyroreaction kettle.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Embodiment 4
The present embodiment provides a kind of preparation method of negative electrode material, referring to embodiment 1, difference is specific method:
In step (1), 180 DEG C of high-temperature stirring 8h.
In step (3 '), 250 DEG C of pre- carbonization treatment 5h.
In step (3 "), 750 DEG C of high temperature cabonization 8h.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Embodiment 5
The present embodiment provides a kind of preparation method of negative electrode material, referring to embodiment 1, difference is specific method:
In step (1), 230 DEG C of high-temperature stirring 5h.
In step (3 '), 450 DEG C of pre- carbonization treatment 3h.
In step (3 "), 1350 DEG C of high temperature cabonization 6.5h.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Embodiment 6
The present embodiment provides a kind of preparation method of negative electrode material, referring to embodiment 1, difference is specific method:
In step (1), petroleum coke 5kg and phenolic resin 95kg is put into according to soft carbon and hard carbon presoma 5:95 mass ratio
In pyroreaction kettle.
In step (3 '), 350 DEG C of pre- carbonization treatments.
In step (3 "), 950 DEG C of high temperature cabonizations.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Embodiment 7
The present embodiment provides a kind of preparation method of negative electrode material, referring to embodiment 1, difference is specific method:
Asphalt 95kg and epoxy resin 5kg is put into pyroreaction according to soft carbon and hard carbon presoma 95:5 mass ratio
In kettle.
In step (3 '), 400 DEG C of pre- carbonization treatments.
In step (3 "), 1150 DEG C of high temperature cabonizations.
What the present embodiment obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Comparative example 1
Referring to embodiment 1, difference is the specific method of this comparative example, and in step (1), the drip of soft carbon presoma coal is only added
Green 100kg is added without hard carbon presoma.
What this comparative example obtained is soft carbon negative electrode material, and test result is shown in Table 1.
Comparative example 2
Referring to embodiment 1, difference is the specific method of this comparative example, and in step (1), hard carbon presoma sucrose is only added
100kg is added without soft carbon presoma.
What this comparative example obtained is hard carbon cathode material, and test result is shown in Table 1.
Fig. 3 is curve graph of the negative electrode material that is prepared of embodiment 3, comparative example 1 and comparative example 2 to lithium charge and discharge, by
The figure can be seen that negative electrode material prepared by embodiment 3, gram relative to comparative example 1 and comparative example 2, within the scope of 0.3~0V
Capacity has a degree of raising；Voltage change is more gentle, and from the point of view of Q=C* △ V, the cathode of embodiment 3 has more
Big specific capacitance.
Comparative example 3
Referring to embodiment 1, difference is for the specific method of this comparative example, in step (1), to coal tar pitch and sucrose without
Melting mixing, and the operation for carrying out step (2) is only directly stirred evenly at normal temperature.
What this comparative example obtained is soft or hard carbon compound cathode materials, and test result is shown in Table 1.
Table 1
Based on the above embodiments with comparative example it is found that the soft or hard carbon compound cathode materials that method of the invention is prepared, tool
There is higher initial charge efficiency；With lithium-ion capacitor prepared by this negative electrode material there is low internal resistance and high capacity to protect
Holdup.Comparative example does not use the solution of the present invention, thus can not obtain excellent results of the invention.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (30)
1. a kind of preparation method of negative electrode material, which is characterized in that the described method comprises the following steps:
(1) soft carbon presoma and hard carbon presoma are heated, carries out melting mixing, obtains mixture；
(2) mixture obtained to step (1) is granulated, and obtains cathode presoma；
(3) carbonization treatment is carried out to step (2) the cathode presoma, obtains the negative electrode material；
In step (1), the soft carbon presoma is coal tar pitch and/or asphalt；In step (1), the hard carbon presoma is
Sucrose；
In step (2), the method for the granulation is multistage atomizing granulation；
In step (3), the carbonization treatment the following steps are included:
Step (2) the cathode presoma is carried out pre- carbonization treatment by (3 ') under nitrogen atmosphere and/or argon atmosphere, is obtained pre-
Char-forming material；
Step (3 ') the pre- char-forming material is carbonized by (3 ") under nitrogen atmosphere and/or argon atmosphere, obtains the cathode material
Material.
2. the method according to claim 1, wherein the temperature of the heating is 180 DEG C~230 in step (1)
℃。
3. the method according to claim 1, wherein in step (1), the melting mixing in a kettle into
Row.
4. the method according to claim 1, wherein the melting mixing is also with stirring.
5. the method according to claim 1, wherein the time of the melting mixing is 5h~8h.
6. the method according to claim 1, wherein the soft carbon presoma is coal tar pitch in step (1).
7. the method according to claim 1, wherein the coal tar pitch is isotropic pitch.
8. the method according to claim 1, wherein the softening point of the coal tar pitch is 75 DEG C~95 DEG C.
9. the method according to claim 1, wherein the degree of graphitization of the coal tar pitch is 50%~80%.
10. the method according to claim 1, wherein the fusing point of the sucrose is 160 DEG C~180 DEG C.
11. the method according to claim 1, wherein purity >=99.7% of the sucrose.
12. the method according to claim 1, wherein in step (1), the soft carbon presoma and hard carbon forerunner
The mass ratio of body is 5:95~95:5.
13. according to the method for claim 12, which is characterized in that in step (1), the soft carbon presoma and hard carbon forerunner
The mass ratio of body is 3:7~7:3.
14. the method according to claim 1, wherein obtained cathode presoma is spherical in step (2)
Grain.
15. the method according to claim 1, wherein the D50 of obtained cathode presoma is 10 in step (2)
μm~30 μm.
16. the method according to claim 1, wherein in step (3 '), the nitrogen atmosphere and/or argon gas gas
Atmosphere is nitrogen atmosphere.
17. the method according to claim 1, wherein in step (3 '), the pre- carbonization in carbide furnace into
Row.
18. the method according to claim 1, wherein the temperature of the pre- carbonization is 250 DEG C in step (3 ')
~450 DEG C.
19. according to the method for claim 18, which is characterized in that in step (3 '), the temperature of the pre- carbonization is 350 DEG C
~400 DEG C.
20. the method according to claim 1, wherein in step (3 '), the time of the pre- carbonization be 3h~
5h。
21. the method according to claim 1, wherein in step (3 "), the nitrogen atmosphere and/or argon gas gas
Atmosphere is nitrogen atmosphere.
22. the method according to claim 1, wherein the carbonization carries out in tube furnace in step (3 ").
23. the method according to claim 1, wherein in step (3 "), the temperature of the carbonization is 750 DEG C~
1350℃。
24. according to the method for claim 23, which is characterized in that in step (3 "), the temperature of the carbonization is 950 DEG C~
1150℃。
25. the method according to claim 1, wherein the time of the carbonization is 5h~8h in step (3 ").
26. the method according to claim 1, wherein the method also includes step (4): step (3) is obtained
The negative electrode material by crushing, classification processing after obtain purification negative electrode material.
27. the method according to claim 1, wherein the described method comprises the following steps:
(1) coal tar pitch and sucrose are added in reaction kettle with the ratio of 3:7~7:3, in 180 DEG C~230 DEG C and stirring condition
Under, melting mixing 5h~8h obtains mixture；The coal tar pitch is isotropic pitch, and softening point is 75 DEG C~95 DEG C, graphite
Change degree is 50%~80%；The fusing point of the sucrose is 160 DEG C~180 DEG C, purity >=99.7%；
(2) mixture obtained to step (1) carries out atomization granulation, obtains cathode presoma；The cathode presoma is spherical shape
Particle, D50 are 10 μm~30 μm；
(3 ') by under step (2) the cathode presoma nitrogen atmosphere in carbide furnace with 350 DEG C~400 DEG C pre- carbonization 3h~
5h obtains pre- char-forming material；
(3 ") by step (3 ') the pre- char-forming material in a nitrogen atmosphere in tube furnace with 950 DEG C~1150 DEG C carbonization 5h~
8h obtains the negative electrode material；
(4) by the negative electrode material that step (3 ") obtains by crushing, purification negative electrode material is obtained after classification processing.
28. the negative electrode material of -27 described in any item method preparations according to claim 1, which is characterized in that the negative electrode material
For the composite negative pole material comprising soft carbon and hard carbon, wherein soft carbon and hard carbon are mutually mixed, dispersed distribution.
29. negative electrode material according to claim 28, which is characterized in that the negative electrode material is lithium-ion capacitor cathode material
Material.
30. a kind of capacitor, which is characterized in that the capacitor includes negative electrode material described in claim 28.
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| CN108975302A (en) * | 2018-07-05 | 2018-12-11 | 中冶焦耐(大连)工程技术有限公司 | A kind of preparation method and application of the low graphitized carbon material of asphaltic base |
| CN110817833A (en) * | 2018-08-09 | 2020-02-21 | 宝武炭材料科技有限公司 | Preparation method of resin-based hard carbon negative electrode material |
| CN109244465B (en) * | 2018-10-10 | 2021-05-28 | 中钢集团鞍山热能研究院有限公司 | Preparation method of negative electrode material |
| CN109494082A (en) * | 2018-11-19 | 2019-03-19 | 中物院成都科学技术发展中心 | A kind of N doping porous graphite alkenes carbon nanosheet material and its preparation method and application |
| CN111244453B (en) * | 2018-11-28 | 2022-03-08 | 上海杉杉科技有限公司 | Artificial composite graphite negative electrode material, lithium ion battery, preparation method and application |
| CN111232970B (en) * | 2018-11-28 | 2023-04-14 | 上海杉杉科技有限公司 | Graphite negative electrode material, lithium ion battery, preparation method and application |
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| CN111293301B (en) * | 2020-03-17 | 2022-06-24 | 江苏科技大学 | Soft and hard carbon composite porous negative electrode material for sodium ion battery and preparation method thereof |
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