CN106698391A - Hard carbon particles prepared with kelp as carbon source, and preparation method and application thereof - Google Patents
Hard carbon particles prepared with kelp as carbon source, and preparation method and application thereof Download PDFInfo
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- CN106698391A CN106698391A CN201710040290.6A CN201710040290A CN106698391A CN 106698391 A CN106698391 A CN 106698391A CN 201710040290 A CN201710040290 A CN 201710040290A CN 106698391 A CN106698391 A CN 106698391A
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- 241000512259 Ascophyllum nodosum Species 0.000 title claims abstract description 48
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 13
- 230000004087 circulation Effects 0.000 abstract description 5
- 239000007773 negative electrode material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011734 sodium Substances 0.000 description 11
- 239000004033 plastic Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses hard carbon particles prepared with kelp as a carbon source, and also discloses a preparation method of the hard carbon particles and an application of the hard carbon particles in a sodium ion battery negative electrode material. The preparation method takes the kelp as a raw material, and the hard carbon particles (KHC) are obtained through acid treatment and high temperature pyrolysis; when used as the sodium ion battery negative electrode material, the prepared hard carbon particles show excellent electrochemical performance, and the specific capacity is still stabilized at 96 mAh*g<-1> at the current density of 1000 mA*g<-1>, while at the current density of 200 mA*g<-1>, the specific capacity is still 205 mAh*g<-1> after circulation is performed for 300 cycles; in addition, the preparation method has the advantages of simple process, low costs of the used raw materials, environmental friendliness and reproduction, and can be applied to large scale production.
Description
Technical field
The present invention relates to one kind with sea-tangle as carbon source obtained in hard carbon particle, further relate to the preparation method of above-mentioned hard carbon particle
And the application of the hard carbon particle in terms of anode material of lithium-ion battery.
Background technology
Lithium ion battery because its energy density is high, having extended cycle life and being widely used in portable electric appts, mixing
Power vehicle and pure electric automobile field.But, uneven (the main collection of the earth's crust content low (0.0065%) of lithium, geographical distribution
In in South America), high cost ($ 5000/ton) the shortcomings of cause that lithium ion battery cannot meet the increasingly increased extensive energy
Storage demand.In recent years, sodium-ion battery receives much attention as the substitute of lithium ion battery, and this is primarily due to sodium ion electricity
Pond has that cost of material is cheap, aboundresources, advantages of environment protection.So far, people have prepared various sodium ions
Cell positive material, and the development of its negative material is relatively slow.Therefore, it is sodium to design and prepare high performance negative material
The task of top priority of ion battery development.Carbon material possesses rich reserves, low cost, environment-friendly, good thermal stability, electrical conductivity
High the advantages of, this becomes a kind of anode material of lithium-ion battery of great prospect.However, most widely used in business
The reversible capacity that graphite is showed when as anode material of lithium-ion battery is but very low.Conversely, the carbon material of some synthesis,
Such as hard carbon, carbon black, petroleum coke, carbon nanocoils, redox graphene, porous carbon/graphene complex, banana skin graphite and stone
Black alkene foam etc. then shows preferably to store up sodium performance.
Wherein, hard carbon has been obtained extensively due to cyclical stability and high rate performance with specific capacity and relative good high
General concern.Nearly the 40% of hard carbon specific capacity all originates from 0.1V (vs Na/Na+) following embedding sodium voltage, so low voltage puts down
Platform makes hard carbon possess voltage window and energy density higher wider as sodium-ion battery.Additionally, hard carbon material also has
Larger interlamellar spacing, so as to show more preferable high rate performance.Different from graphited soft carbon, hard carbon is presented by graphene layer
The formed random graphits structure of expansion, we can adjust the size and layer of random layer crystal body by changing the condition being heat-treated
Spacing.Meanwhile, fundamentally understand biomass derived hard carbon and study its storage sodium performance be significant because this process
Cost of material is low, is conducive to being applied on a large scale.
The content of the invention
Goal of the invention：The technical problems to be solved by the invention are to provide a kind of hard carbon obtained in sea-tangle as carbon source
Grain.
The technical problem also to be solved of the invention is to provide the preparation side of above-mentioned hard carbon particle obtained in sea-tangle as carbon source
Method.
The of the invention technical problem finally to be solved be to provide above-mentioned hard carbon particle obtained in sea-tangle as carbon source sodium from
Application in terms of sub- cell negative electrode material.
The content of the invention：In order to solve the above technical problems, the technology used in the present invention means are：
A kind of hard carbon particle obtained in sea-tangle as carbon source, in the hard carbon particle size of random layer crystal structure be 11.3~
14.4nm, interlamellar spacing is 0.36~0.39nm.
The preparation method of above-mentioned hard carbon particle obtained in sea-tangle as carbon source, comprises the following steps：
Step 1, pre-treatment step：Sea-tangle is cut into after the kelp block of required size and repeatedly washs stand-by；
Step 2, it is 10wt%'s that pretreated the kelp block is sequentially placed into the hydrochloric acid and mass percent that concentration is 6M
Stirring a period of time is impregnated in hydrofluoric acid, is then cleaned again, dried process；
Step 3, the kelp block after step 2 is processed is placed in tube furnace, under argon gas atmosphere, is first incubated at 30 DEG C
30min, is then warming up at 900~1600 DEG C with the heating rate of 5 DEG C/min and is heat-treated 2h, obtains required target product.
Wherein, in step 1, every piece of size of the kelp block is 1cm × 1cm.
Wherein, in step 1, the kelp block first impregnates stirring 6 hours in concentration is for the hydrochloric acid of 6M, then again by sea-tangle
Block is placed in the hydrofluoric acid that mass percent is 10wt% and impregnates stirring 15 hours.
Wherein, in step 2, by the kelp block cleaning after being vacuum dried 24h at 120 DEG C.
Wherein, in step 2, the kelp block is warming up to 900 DEG C, 1300 DEG C and 1600 respectively with the heating rate of 5 DEG C/min
2h is heat-treated at DEG C and obtains three kinds of hard carbon particles KHC-900, KHC-1300 and KHC-1600.
Above-mentioned application of the hard carbon particle in terms of anode material of lithium-ion battery obtained in sea-tangle as carbon source.
Compared to prior art, technical solution of the present invention have the advantage that for：
Hard carbon particle obtained in sea-tangle as carbon source of the invention has excellent chemical property；Preparation method of the present invention with
Sea-tangle is raw material, and hard carbon particle (KHC) is obtained by acid treatment and high temperature pyrolysis, the method have process is simple, mild condition,
The advantage that reaction time is short, favorable reproducibility, safe operation, yield are high, can be applied to large-scale production.
Brief description of the drawings
Fig. 1 a~1d is respectively the SEM figures of once purged sea-tangle, KHC-900, KHC-1300 and KHC-1600；
Fig. 2 is the present invention three kinds of hard carbon particles KHC-900, KHC-1300 and KHC-1600 obtained in sea-tangle as carbon source
XRD；
Fig. 3 a~3c is the present invention three kinds of hard carbon particles KHC-900, KHC-1300 and KHC- obtained in sea-tangle as carbon source
1600 HRTEM figures；
Fig. 4 is the charging and discharging curve figure of KHC-1300 obtained in embodiment 1；
Fig. 5 is voltage range in 0.01-2V vs Na+/ Na, current density is respectively 25,50,100,200,500,
1000mA·g-1When KHC-900, KHC-1300 and KHC-1600 high rate performance figure；
Fig. 6 is the cycle performance figure of KHC-1300 obtained in embodiment 1.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, the content described by embodiment is merely to illustrate
The present invention, without should also without limitation on the present invention described in detail in claims.
Embodiment 1
The preparation method of hard carbon particle obtained in sea-tangle as carbon source of the invention, specifically includes following steps：
Step 1, pre-treatment step：A bulk of sea-tangle that in the market is bought is cut into fritter sea-tangle, ultrasound is then placed in
Running water supersound washing is used in machine, each 30min is repeated three times；Fritter sea-tangle is further cut into size for 1cm
The kelp block of × 1cm, 1cm × 1cm the kelp blocks is transferred in beaker and distills water washing three times with 400mL, stand-by after draining the water；
Step 2, pretreated the kelp block is placed in the hydrochloric acid that 400mL concentration is 6M, and the kelp block is fully immersed in salt
Below acid solution face, 6h is stirred, outwell and taken out after hydrochloric acid drains the kelp block, then the kelp block is put into plastic beaker, toward plastics
The hydrofluoric acid that 400mL mass percents are 10% is added in cup, the kelp block is fully immersed in below hydrofluoric acid liquid level, stirred
15h；Outwell after hydrofluoric acid drains the kelp block, to 300mL distilled water is added in plastic beaker, water is changed after ultrasonic 10min, repeatedly
Carry out five times, take out after the kelp block is drained and be placed in glass beaker, in being vacuum dried 24h at 120 DEG C；
Step 3, the dried the kelp block of step 2 is placed in tube furnace, under argon gas atmosphere, is first incubated at 30 DEG C
30min, target product KHC-1300 is obtained after the 2h that is carbonized at being then warming up to 1300 DEG C with the heating rate of 5 DEG C/min.
As shown in Figure 1a, the sea-tangle after cleaning is to be about 100 μm, thick about 20 μm laminated structure, as illustrated in figure 1 c, through carbon
The hard carbon KHC-1300 obtained after change is also laminated structure, but size is small a lot；As shown in Fig. 2 KHC-1300 is non-graphite
The carbon of change；As shown in Figure 3 b, KHC-1300 is made up of the random layer nanocrystal of shortrange order, and interlamellar spacing is 0.39nm or so, and
The lattice of random layer nanocrystal is expanded, shrinks repeatedly during embedding removing sodium, and spacing of lattice is arrived 3.9Between convert.
KHC-1300 obtained in embodiment 1 is tested as the performance of anode material of lithium-ion battery, detailed process
It is as follows：The test of chemical property uses CR2032 batteries.Using N-METHYLFORMAMIDE as solvent, by obtained in embodiment 1
Be applied to for the mixed material even slurry of gained with 8: 1: 1 ratio ground and mixed by KHC-1300 and carbon black, Kynoar
Dried in vacuum overnight on Cu paper tinsels and at being placed on 80 DEG C, the load capacity of electrode slice is 0.8-1.2mgcm-2；Electrolyte be by
A certain amount of lmol/L NaClO4Volume ratio is dissolved in in 1: 1 ethylene carbonate and the mixed solution of diethyl carbonate；Adopt
With the glass fibre and pure sodium metal foil of Whatman respectively as barrier film and to electrode；All operations about battery are all being filled
Glove box (the H of full argon gas atmosphere2O, O2＜ 0.1ppm) in carry out；The constant current charge-discharge test of battery is at room temperature, electric with indigo plant
CT2001A multi-channel battery test systems, in 0.01-2V vs Na+Enter under different current densities in the range of/Na fixed voltages
OK, as a result as shown in Fig. 4~Fig. 6.
Wherein, Fig. 4 is the charging and discharging curve figure of KHC-1300, as shown in figure 4, the initial discharge capacity of KHC-1300 is
521mAh·g-1, charging capacity is 334mAhg-1；As shown in figure 5, compared to KHC-900 and KHC-1600, KHC-1300
High rate performance is the most excellent；As shown in fig. 6, the stable cycle performance of KHC-1300, after through 300 circle circulations its capacity almost without
Decay (25mAg-1Lower circulation 10 is enclosed, 50mAg-1Lower circulation 20 is enclosed, then 200mAg-1Lower circulation 270 is enclosed).
Embodiment 2
The preparation method of hard carbon particle obtained in sea-tangle as carbon source of the invention, specifically includes following steps：
Step 1, pre-treatment step：A bulk of sea-tangle that in the market is bought is cut into fritter sea-tangle, ultrasound is then placed in
Running water supersound washing is used in machine, each 30min is repeated three times；Fritter sea-tangle is further cut into size for 1cm
The kelp block of × 1cm, 1cm × 1cm the kelp blocks is transferred in beaker and distills water washing three times with 400mL, stand-by after draining the water；
Step 2, pretreated the kelp block is placed in the hydrochloric acid that 400mL concentration is 6M, and the kelp block is fully immersed in salt
Below acid solution face, 6h is stirred, outwell and taken out after hydrochloric acid drains the kelp block, then the kelp block is put into plastic beaker, toward plastics
The hydrofluoric acid that 400mL mass percents are 10% is added in cup, the kelp block is fully immersed in below hydrofluoric acid liquid level, stirred
15h；Outwell after hydrofluoric acid drains the kelp block, to 300mL distilled water is added in plastic beaker, water is changed after ultrasonic 10min, repeatedly
Carry out five times, take out after the kelp block is drained and be placed in glass beaker, in being vacuum dried 24h at 120 DEG C；
Step 3, the dried the kelp block of step 2 is placed in tube furnace, under argon gas atmosphere, is first incubated at 30 DEG C
30min, target product KHC-900 is obtained after the 2h that is carbonized at being then warming up to 900 DEG C with the heating rate of 5 DEG C/min.
As shown in Figure 1 b, the KHC-900 for being obtained after carbonization is laminated structure, small compared to 1a sizes a lot；Such as Fig. 2
Shown, KHC-900 is non-graphitized carbon；As shown in Figure 3 a, gained hard carbon KHC-900 by shortrange order random layer nanocrystal
Constitute, interlamellar spacing is 0.39nm.
KHC-900 obtained in embodiment 2 is tested as the performance of anode material of lithium-ion battery, detailed process is such as
Under：The test of chemical property uses CR2032 batteries.Using N-METHYLFORMAMIDE as solvent, by KHC- obtained in embodiment 2
900 with carbon black, Kynoar with 8: 1: 1 ratio ground and mixed, the mixed material even slurry of gained is applied to Cu paper tinsels
Dried in vacuum overnight at going up and being placed on 80 DEG C, the load capacity of electrode slice is 0.8-1.2mgcm-2；Electrolyte is will be certain
The 1mol/L NaClO of amount4Volume ratio is dissolved in in 1: 1 ethylene carbonate and the mixed solution of diethyl carbonate；Using
The glass fibre of Whatman and pure sodium metal foil are respectively as barrier film and to electrode；All operations about battery are all being full of
Glove box (the H of argon gas atmosphere2O, O2＜ 0.1ppm) in carry out；The constant current charge-discharge test of battery is at room temperature, electric with indigo plant
CT2001A multi-channel battery test systems, in 0.01-2V vs Na+Enter under different current densities in the range of/Na fixed voltages
OK, as a result as shown in Figure 5.
As shown in figure 5, under low current density, the specific capacity of KHC-900 is minimum, less than KHC-1300 and KHC-1600；
At higher current densities, its specific capacity is less than KHC-1300, higher than KHC-1600.
Embodiment 3
The preparation method of hard carbon particle obtained in sea-tangle as carbon source of the invention, specifically includes following steps：
Step 1, pre-treatment step：A bulk of sea-tangle that in the market is bought is cut into fritter sea-tangle, ultrasound is then placed in
Running water supersound washing is used in machine, each 30min is repeated three times；Fritter sea-tangle is further cut into size for 1cm
The kelp block of × 1cm, 1cm × 1cm the kelp blocks is transferred in beaker and distills water washing three times with 400mL, stand-by after draining the water；
Step 2, pretreated the kelp block is placed in the hydrochloric acid that 400mL concentration is 6M, and the kelp block is fully immersed in salt
Below acid solution face, 6h is stirred, outwell and taken out after hydrochloric acid drains the kelp block, then the kelp block is put into plastic beaker, toward plastics
The hydrofluoric acid that 400mL mass percents are 10% is added in cup, the kelp block is fully immersed in below hydrofluoric acid liquid level, stirred
15h；Outwell after hydrofluoric acid drains the kelp block, to 300mL distilled water is added in plastic beaker, water is changed after ultrasonic 10min, repeatedly
Carry out five times, take out after the kelp block is drained and be placed in glass beaker, in being vacuum dried 24h at 120 DEG C；
Step 3, the dried the kelp block of step 2 is placed in tube furnace, under argon gas atmosphere, is first incubated at 30 DEG C
30min, target product KHC-1600 is obtained after the 2h that is carbonized at being then warming up to 1600 DEG C with the heating rate of 5 DEG C/min.
As shown in Figure 1 d, the KHC-1600 for being obtained after carbonization is laminated structure, small compared to 1a sizes a lot；As schemed
Shown in 2, KHC-1600 is non-graphitized carbon；As shown in Figure 3 c, gained hard carbon KHC-1600 by shortrange order random layer nanometer
Crystal is constituted, and interlamellar spacing is 0.36nm.
KHC-1600 obtained in embodiment 3 is tested as the performance of anode material of lithium-ion battery, detailed process
It is as follows：The test of chemical property uses CR2032 batteries.Using N-METHYLFORMAMIDE as solvent, by obtained in embodiment 3
Be applied to for the mixed material even slurry of gained with 8: 1: 1 ratio ground and mixed by KHC-1600 and carbon black, Kynoar
Dried in vacuum overnight on Cu paper tinsels and at being placed on 80 DEG C, the load capacity of electrode slice is 0.8-1.2mgcm-2；Electrolyte be by
A certain amount of 1mol/L NaClO4Volume ratio is dissolved in in 1: 1 ethylene carbonate and the mixed solution of diethyl carbonate；Adopt
With the glass fibre and pure sodium metal foil of Whatman respectively as barrier film and to electrode；All operations about battery are all being filled
Glove box (the H of full argon gas atmosphere2O, O2＜ 0.1ppm) in carry out；The constant current charge-discharge test of battery is at room temperature, electric with indigo plant
CT2001A multi-channel battery test systems, in 0.01-2V vs Na+Enter under different current densities in the range of/Na fixed voltages
OK, as a result as shown in Figure 5.
As shown in figure 5, under low current density, the specific capacity of KHC-1600 is less than KHC-1300, higher than KHC-900；
Under high current density, its specific capacity is minimum, less than KHC-900 and KHC-1300.
Therefore it is the most excellent compared to the high rate performance and cyclical stability of KHC-900 and KHC-1600, KHC-1300：
1000mA·g-1Current density under its specific capacity remain to stabilization in 96mAhg-1, and in 200mAg-1Current density under,
Its specific capacity still has 205mAhg after 300 circle circulations-1。
With the rising of carburizing temperature, the interlamellar spacing of KHC-900, KHC-1300, KHC-1600 is gradually reduced, respectively
0.39nm, 0.39nm, 0.36nm, the decline of interlamellar spacing are unfavorable for the storage of sodium ion；Simultaneously with the rising of carburizing temperature,
The oxygen content of tri- kinds of hard carbon particles of KHC-900, KHC-1300, KHC-1600 is gradually reduced, be followed successively by 16.6at.%,
11.6at.%, 10.3at.% (at.% is atom content percentage), the decline of oxygen content can reduce the energy of sodium ion diffusion
Build, be conducive to the storage of sodium ion, in sum, its best performance when KHC-1300 is as anode material of lithium-ion battery.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to of the invention
The restriction of implementation method.For those of ordinary skill in the field, it can also be made on the basis of the above description
The change or variation of its multi-form.There is no need and unable to be exhaustive to all of implementation method.And these belong to this hair
Obvious change that bright spirit is extended out or among changing still in protection scope of the present invention.
Claims (7)
1. one kind hard carbon particle obtained in sea-tangle as carbon source, it is characterised in that：The chi of random layer crystal structure in the hard carbon particle
Very little is 11.3~14.4nm, and interlamellar spacing is 0.36~0.39nm.
2. the preparation method of hard carbon particle obtained in sea-tangle as carbon source described in a kind of claim 1, it is characterised in that including such as
Lower step：
Step 1, pre-treatment step：Sea-tangle is cut into after the kelp block of required size and repeatedly washs stand-by；
Step 2, it is the hydrogen fluorine of 10wt% that pretreated the kelp block is sequentially placed into the hydrochloric acid and mass percent that concentration is 6M
Stirring a period of time is impregnated in acid, is then cleaned again, dried process；
Step 3, the kelp block after step 2 is processed is placed in tube furnace, under argon gas atmosphere, is first incubated 30min at 30 DEG C,
Then it is warming up at 900~1600 DEG C with the heating rate of 5 DEG C/min and is heat-treated 2h, obtains required target product.
3. the preparation method of hard carbon particle obtained in sea-tangle as carbon source according to claim 2, it is characterised in that：Step
In 1, every piece of size of the kelp block is 1cm × 1cm.
4. the preparation method of hard carbon particle obtained in sea-tangle as carbon source according to claim 2, it is characterised in that：Step
In 2, the kelp block first impregnates stirring 6 hours in concentration is for the hydrochloric acid of 6M, and the kelp block then is placed in into mass percent again
To impregnate stirring 15 hours in the hydrofluoric acid of 10wt%.
5. the preparation method of hard carbon particle obtained in sea-tangle as carbon source according to claim 2, it is characterised in that：Step
In 2, by the kelp block cleaning after being vacuum dried 24h at 120 DEG C.
6. the preparation method of hard carbon particle obtained in sea-tangle as carbon source according to claim 2, it is characterised in that：Step
2h is heat-treated in 3, at the kelp block is warming up into 900 DEG C, 1300 DEG C and 1600 DEG C respectively with the heating rate of 5 DEG C/min obtain three
Plant hard carbon particle KHC-900, KHC-1300 and KHC-1600.
7. application of the hard carbon particle in terms of anode material of lithium-ion battery obtained in sea-tangle as carbon source described in claim 1.
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| CN107579249A (en) * | 2017-08-30 | 2018-01-12 | 重庆云天化瀚恩新材料开发有限公司 | A kind of Chinese medicine slag prepares hard carbon cathode material and preparation method thereof |
| CN112290025A (en) * | 2020-11-11 | 2021-01-29 | 瓮福（集团）有限责任公司 | Preparation method of electrode material based on carbonized kelp and lithium-sulfur battery |
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| CN106033813A (en) * | 2016-06-08 | 2016-10-19 | 陕西科技大学 | Method for preparing sodium-ion battery negative electrode material with sodium alga acid as carbon source |
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