CN117023559A - Hard carbon material, preparation method thereof and negative electrode plate - Google Patents
Hard carbon material, preparation method thereof and negative electrode plate Download PDFInfo
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- CN117023559A CN117023559A CN202311052049.7A CN202311052049A CN117023559A CN 117023559 A CN117023559 A CN 117023559A CN 202311052049 A CN202311052049 A CN 202311052049A CN 117023559 A CN117023559 A CN 117023559A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 99
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 150000003505 terpenes Chemical class 0.000 claims abstract description 34
- 235000007586 terpenes Nutrition 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 239000007833 carbon precursor Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007773 negative electrode material Substances 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon material, a preparation method thereof and a negative electrode plate. The preparation method of the hard carbon material comprises the following steps: s1, pretreating a mixture of terpene resin, graphene oxide and a cross-linking agent to obtain a hard carbon precursor; s2, performing high-temperature carbonization treatment on the mixture of the hard carbon precursor and the pore-forming agent to obtain the hard carbon material. According to the invention, terpene resin and graphene oxide are used as raw materials, and under the action of a cross-linking agent and a pore-forming agent, a hard carbon material with low production cost, adjustable pore diameter and pore volume, excellent initial performance, excellent capacity performance and excellent capacity retention rate can be obtained; the negative electrode material is used for the negative electrode material of the sodium ion battery, so that the production cost of the battery can be further reduced, and the battery is endowed with excellent multiplying power performance and cycle performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon material, a preparation method thereof and a negative electrode plate.
Background
As the price of lithium carbonate increases, the demand for sodium ion batteries increases. At present, a graphite negative electrode used in a lithium ion battery cannot be directly used in a sodium ion battery, the radius of sodium ions is larger than that of lithium ions, the interlayer spacing of the graphite negative electrode is narrower, enough sodium ions cannot be inlaid, and the gram capacity of the battery is extremely low. Amorphous carbon is a common sodium ion battery negative electrode material, wherein a hard carbon negative electrode is mainly used, and a soft carbon negative electrode is auxiliary.
Hard carbon materials can be broadly classified into three types of resin-based, pitch-based and bio-based. The resin-based hard carbon material has the advantages of reliable performance, standard consistency, relatively fewer impurities, high raw material cost and low carbon extraction efficiency due to easy volatilization in the processing process. The asphalt-based hard carbon material has wide obtaining channel and low cost, and each ton of unit price can reach about 2 ten thousand yuan, but the initial efficiency performance and the energy density performance are general. The bio-based hard carbon material has the characteristics of mature process, excellent performance, good consistency and the like, and the precursor can be carbon-containing biomass such as coconut husk, starch, vinasse and the like, and has the defect of relatively high cost. It is therefore an urgent need to find a low cost, high performance, and batch stable sodium-electric hard carbon material.
The conventional resin hard carbon refers to phenolic resin, such as phenol-formaldehyde resin, m-diphenol-formaldehyde resin, p-diphenol-formaldehyde resin, phenol-furfural resin and the like, and the hard carbon is manufactured by adopting the resin at a high cost, so that the current market demand cannot be met.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a method for preparing a hard carbon material, which can greatly reduce the production cost and obtain a high-performance hard carbon material with adjustable pore diameter and pore volume.
A second object of the present invention is to provide a hard carbon material which is inexpensive and has excellent initial performance, capacity performance and capacity retention.
A third object of the present invention is to provide a negative electrode tab comprising a hard carbon material as described above.
In order to achieve the above object of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of a hard carbon material, which comprises the following steps:
s1, pretreating a mixture of terpene resin, graphene oxide and a cross-linking agent to obtain a hard carbon precursor;
s2, performing high-temperature carbonization treatment on the mixture of the hard carbon precursor and the pore-forming agent to obtain the hard carbon material.
In step S1, the softening point of the terpene resin is 50-140 ℃, and the carbon residue rate is 5-12%.
Preferably, in step S1, the number of layers of the graphene oxide is 1-5, the sheet diameter is <20 μm, the oxygen content is <30wt%, and ID/IG >0.8.
Preferably, in step S1, the crosslinking agent includes at least one of monoammonium phosphate, phosphorus pentoxide, dopamine, thiourea, and maleic anhydride.
Further, in step S1, the mass ratio of the terpene resin, the graphene oxide, and the crosslinking agent is (2 to 6): (0.5-1.5): (0.5-1.5).
Further, in step S1, grinding is further included before the pretreatment.
Preferably, in step S1, the milling comprises ball milling.
Preferably, in step S1, the grinding speed is 100-800 rmp, and the grinding time is 1-3 hours.
Further, in step S1, the preprocessing includes: heating to 280-410 deg.c in inert atmosphere for heat preservation for 0.5-4 hr and cooling.
Preferably, in step S1, the rate of temperature rise is 1-10 ℃/min.
Further, in step S2, the pore-forming agent includes KOH, naOH, C 2 H 5 ONa and C 2 H 5 At least one of OK.
Preferably, in step S2, the mass ratio of the hard carbon precursor to the pore-forming agent is (3-8): 1.
further, in step S2, grinding is further included before the high-temperature carbonization treatment.
Preferably, in step S2, the milling comprises ball milling.
Preferably, in step S2, the grinding speed is 200-1500 rmp, and the grinding time is 1-3 h.
Further, in step S2, the high-temperature carbonization includes: heating to 1300-1600 ℃ under inert atmosphere, and preserving heat for 2-12 h.
Preferably, in step S2, the temperature rising rate is 3-15 ℃/min.
The invention also provides a hard carbon material prepared by the preparation method of the hard carbon material.
The invention also provides a negative electrode plate which comprises the hard carbon material.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, terpene resin is taken as a framework, and graphene oxide is compounded, so that a high-performance hard carbon material with adjustable pore diameter and pore volume can be obtained under the action of a cross-linking agent and a pore-forming agent; terpene resin is used as a raw material, the cost is low, and the production cost can be greatly reduced; the prepared hard carbon material has excellent initial performance, capacity performance and capacity retention rate; the hard carbon material provided by the invention is used as the negative electrode material of the sodium ion battery, so that the production cost of the battery can be further reduced, and the battery is endowed with excellent multiplying power performance and cycle performance.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes a hard carbon material, a preparation method thereof and a negative electrode plate.
In some embodiments of the present invention, there is provided a method for preparing a hard carbon material, comprising the steps of:
s1, pretreating a mixture of terpene resin, graphene oxide and a cross-linking agent to obtain a hard carbon precursor;
s2, performing high-temperature carbonization treatment on the mixture of the hard carbon precursor and the pore-forming agent to obtain the hard carbon material.
The terpene resin is used as petrochemical products, has a certain degree of polymerization carbon component, can be independently used as a precursor skeleton for preparing hard carbon, is compounded by adding the graphene oxide material, and can be fully combined to improve the hard carbon performance; adding a cross-linking agent for doping and cross-linking reaction, further improving the cross-linking degree and polymerization degree of the product, and ensuring the yield and performance of the hard carbon material. Meanwhile, the crosslinked terpene resin and graphene oxide composite product is added with a pore-forming agent to perform pore-forming, so that the pore size distribution and pore volume can be improved.
The invention uses terpene resin as raw material, has low cost and can greatly reduce the production cost.
The hard carbon material prepared by the preparation method of the hard carbon material has excellent initial performance, capacity performance and capacity retention rate.
According to the preparation method of the hard carbon material, the pore volume and the pore size of the hard carbon can be regulated and controlled through the pore-forming agent.
In some embodiments of the invention, in step S1, the terpene resin has a softening point of 50-140 ℃ and a carbon residue rate of 5-12%; preferably, the terpene resin has a softening point of 80 to 140 ℃; more preferably, the terpene resin has a softening point of 120 to 140 ℃ and a carbon residue ratio of 8 to 12%.
The terpene resin is prepared by processing natural turpentine, and the softening point is 50-140 ℃; terpenes are easy to undergo cyclization, oxidation, reduction, polymerization and other reactions; terpenes can also undergo intramolecular rearrangements and ethylenic translocation; an ideal hard carbon material can be obtained.
The structure of the terpene resin is as follows:
in some embodiments of the present invention, in step S1, the terpene resin comprises a liquid-based terpene resin and/or a solid terpene resin.
In some embodiments of the present invention, in step S1, the number of graphene oxide layers is 1 to 5, and the sheet diameter is<20 μm, oxygen content<30wt％，I D /I G >0.8; preferably, the number of layers of the graphene oxide is 1-3, and the sheet diameter is equal to that of the graphene oxide<12 μm, oxygen content<25wt％，I D /I G >1.1；I D /I G Is the ratio of the D peak intensity to the G peak intensity in the raman spectrum.
According to the invention, the terpene resin and the graphene oxide are used as raw materials for preparing the hard carbon material, and the terpene resin and the graphene oxide with the parameters are used for improving the performance of the hard carbon material.
In some embodiments of the present invention, in step S1, the crosslinking agent includes at least one of monoammonium phosphate, phosphorus pentoxide, dopamine, thiourea, and maleic anhydride; preferably, the crosslinking agent comprises monoammonium phosphate ((NH) 4 ) 2 HPO 4 ) And/or maleic anhydride.
The cross-linking agent is adopted for doping and cross-linking, so that the polymerization degree of the prepared hard carbon material can be improved.
In some embodiments of the present invention, in step S1, the mass ratio of terpene resin, graphene oxide, and crosslinking agent is (2 to 6): (0.5-1.5): (0.5-1.5); preferably, the mass ratio of terpene resin, graphene oxide and cross-linking agent is (2-4): (0.8-1.2): (0.8-1.2).
In some embodiments of the invention, in step S1, grinding is further included before the pretreatment.
In some embodiments of the invention, in step S1, milling comprises ball milling; preferably, the grinding speed is 100-800 rmp, and the grinding time is 1-3 h; preferably, the grinding speed is 300-500 rmp, and the grinding time is 1.5-3 h.
In some embodiments of the present invention, in step S1, the preprocessing includes: heating to 280-410 ℃ under inert atmosphere, preserving heat for 0.5-4 h, and cooling; typical, but not limiting, for example, the temperature of the pretreatment may be 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 410 ℃, or a range of values consisting of any two thereof; the pretreatment time is 0.5h, 1h, 1.5h, 2.5h, 3h, 3.5h, 4h or a range of values consisting of any two of these. Preferably, the pretreatment temperature is 300-410 ℃ and the pretreatment time is 0.5-2 h.
In some embodiments of the invention, in step S1, the rate of temperature rise during the pretreatment is 1-10 ℃/min; preferably, the temperature rising rate of the pretreatment process is 4-6 ℃/min.
In some embodiments of the invention, in step S1, the inert atmosphere comprises nitrogen; preferably, nitrogen is introduced in the pretreatment process; the flow rate of nitrogen is 5 to 300mL/min, preferably 100 to 200mL/min.
According to the invention, through ball milling, terpene resin, graphene oxide and a cross-linking agent can be fully contacted and uniformly mixed; the mixture is carbonized and pretreated, so that most of moisture and easily broken elements can be removed; moreover, the carbonization pretreatment can form holes on the surface of the carbon material; under the initiation of cross-linking agent, the cross-linking reaction can be carried out to form macromolecular compound with more pore structures and more macropores.
In some embodiments of the invention, in step S2, the pore-forming agent comprises KOH, naOH, C 2 H 5 ONa and C 2 H 5 At least one of OK.
In some embodiments of the invention, in step S2, the mass ratio of the hard carbon precursor and the pore-forming agent is (3-8): 1, a step of; typically, but not by way of limitation, the mass ratio of hard carbon precursor to pore former may be 3:1. 4: 1.5:1. 6: 1. 7: 1. 8:1 or any two thereof.
The pore volume and the pore diameter of the hard carbon material are regulated and controlled by adopting the pore-forming agent, and the porous structure of the hard carbon material has proper pore volume and pore diameter, thereby being beneficial to improving the performances of gram volume, first efficiency and the like of the hard carbon material.
In some embodiments of the present invention, grinding is further included before the high temperature carbonization treatment in step S2.
In some embodiments of the invention, in step S2, milling comprises ball milling; preferably, the grinding speed is 200-1500 rmp, and the grinding time is 1-3 h; preferably, the grinding speed is 600-1000 rmp, and the grinding time is 2-3 h.
In some embodiments of the invention, in step S2, high temperature carbonization comprises: heating to 1300-1600 ℃ under inert atmosphere, and preserving heat for 2-12 h; typical, but not limiting, temperatures for high temperature carbonization may be, for example, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, or a range of any two of these; the high-temperature carbonization time is 2h, 4h, 6h, 8h, 10h, 12h or the range value composed of any two of the two. Preferably, the high-temperature carbonization temperature is 1400-1500 ℃, and the high-temperature carbonization time is 2-8 h.
In some embodiments of the invention, in step S2, the rate of temperature rise during high temperature carbonization is 3-15 ℃/min; preferably, the rate of temperature rise during high temperature carbonization is 5 to 10 ℃/min.
The invention further carries out high-temperature carbonization on the basis of carbonization pretreatment, further deeply performs pore-forming, removes water and most oxygen-containing groups, and internally performs pore-forming on the crosslinked macromolecules to form a structure with edge macropores, interlayer hollows and internal micropores.
The invention adopts proper carbonization temperature, carbonization time and heating rate, which is beneficial to ensuring the performance of the obtained hard carbon material.
In some embodiments of the present invention, in step S2, further comprising pulverizing the hard carbon material; preferably, the D50 of the hard carbon material after comminution is from 5 to 15 μm.
In some embodiments of the present invention, a hard carbon material is also provided, and the hard carbon material is prepared by using the preparation method of the hard carbon material.
In some embodiments of the invention, the hard carbon material has a particle size D10 of 2 to 4.5 μm and a D90 of 10 to 15 μm.
In some embodiments of the invention, the hard carbon material has a moisture content of 0.1 to 0.2wt% and an ash content of 0.5wt% to 0.6wt%.
In some embodiments of the invention, the hard carbon material has a specific surface area (BET) of 2.5 to 3.5m 2 /g。
In some embodiments of the invention, the first effect of the hard carbon material is greater than or equal to 92%, the capacity is greater than or equal to 300mAh/g, and the capacity retention rate after 1C cycle for 50 circles is greater than 98%.
In some embodiments of the invention, a negative electrode sheet is also provided, including the hard carbon material described above.
In some embodiments of the invention, a sodium ion battery is also provided, including the negative electrode tab described above.
The obtained sodium ion battery using the hard carbon material as the negative electrode material has excellent first efficiency, cycle performance and rate capability.
Example 1
The preparation method of the hard carbon material provided by the embodiment comprises the following steps:
s1, terpene resin (softening point is 135 ℃, carbon residue rate is 10%) and graphene oxide (layer number is 3, sheet diameter is 15 μm, oxygen content is 20%, I D /I G =1.5) according to a mass ratio of 3:1 to obtain a mixed material, wherein the mass ratio of the mixed material to the ammonium dihydrogen phosphate is 4:1, ball milling and mixing are carried out in a ball milling tank, the rotation speed of ball milling is 400rpm, and the time is 2 hours; ball milling, placing in corundum crucible of tubular furnace, introducing inert N with flow rate of 130mL/min 2 Atmosphere (purity)>99.9 percent) heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 1 hour, and cooling to room temperature to obtain a hard carbon precursor;
s2, mixing the hard carbon precursor and KOH powder according to a mass ratio of 5:1, ball milling and mixing, wherein the ball milling speed is 800rpm, and the time is 2 hours; ball milling, placing into graphite crucible of tube furnace, adding inert N 2 Atmosphere (purity)>99.9%) and heating to 1450 ℃ at a speed of 8 ℃/min, and then cooling after heat preservation for 5 hours; then, the mixture was pulverized to obtain a hard carbon material having a D50 of 10. Mu.m.
Example 2
The preparation method of the hard carbon material provided in this embodiment is different from that in the embodiment 1, the number of layers of graphene oxide is 2, the sheet diameter is 10 μm, the oxygen content is 22%, and I D /I G ＝2。
Example 3
The preparation method of the hard carbon material provided in this example is different from that in the reference example 1 only in that in the step S1, the softening point of the terpene resin is 75 ℃, and the carbon residue rate is 7%; the number of layers of the graphene oxide is 10, the sheet diameter is 15 mu m, the oxygen content is 30 percent, I D /I G ＝0.8。
Example 4
The preparation method of the hard carbon material provided in this embodiment is different from that in the reference embodiment 1 only in that in the step S1, the mass ratio of terpene resin to graphene oxide is 5:2; the mass ratio of the mixed material to the ammonium dihydrogen phosphate is 3:1.
example 5
The preparation method of the hard carbon material provided in this embodiment is different from that in the embodiment 1, only in that in the step S1, the temperature is raised to 360 ℃ at a rate of 3 ℃/min, the heat is preserved for 4 hours, and then the hard carbon material is cooled to room temperature.
Example 6
The preparation method of the hard carbon material provided in this embodiment is different from that in the reference embodiment 1 only in that in the step S1, the rotation speed of ball milling is 350rpm, and the time is 1.5h; ball milling, placing in corundum crucible of tubular furnace, introducing inert N with flow rate of 100mL/min 2 Atmosphere (purity)>99.9 percent) and heating to 430 ℃ at the speed of 6 ℃/min, and then carrying out heat preservation treatment for 1.5 hours, and cooling to room temperature to obtain the hard carbon precursor.
Example 7
The preparation method of the hard carbon material provided in this embodiment is different from that in the embodiment 1 only in that in the step S2, the temperature is raised to 1350 ℃ at a rate of 8 ℃/min, the heat is preserved for 6.5 hours, and then the hard carbon material is cooled to room temperature.
Example 8
The preparation method of the hard carbon material provided in this example is described with reference to example 1, except that in step S2, ball milling is performed, and then the hard carbon material is put into a graphite crucible of a tube furnace, and inert N is used as the inert gas 2 Atmosphere (purity)>99.9%), heating to 1280 ℃ at a speed of 8 ℃/min, preserving heat for 6 hours, and cooling; then, the mixture was pulverized to obtain a hard carbon material having a D50 of 10. Mu.m.
Comparative example 1
The preparation method of the hard carbon material provided in this comparative example is different from that in the reference example 1 only in that in the step S1, graphene oxide is not added, and terpene resin and monoammonium phosphate are mixed according to a mass ratio of 4:1 ball-milling and mixing in a ball-milling tank.
Comparative example 2
The preparation method of the hard carbon material provided in this comparative example is different from that in the reference example 1 only in that in the step S1, monoammonium phosphate is not added, and terpene resin and graphene oxide are mixed according to a mass ratio of 3:1 ball-milling and mixing in a ball-milling tank.
Test example 1
The preparation method of 2032 electricity buckling comprises the following steps:
and (3) a negative electrode material: conductive agent SP: binder SBR: the mass ratio of the binder CMC is 95.5:1.5:1.5:1.5 homogenizing, coating, and drying to obtain a negative electrode plate with compactness of 1.05g/cm 3 The negative electrode adopts a lithium sheet with the thickness of 600 mu m, electrolyte is added, the negative electrode is assembled into 2032 for buckling, and the negative electrode is packaged for charge and discharge test.
Charge-discharge system: in the interval of 0-2.5V, the constant current of 0.1C is firstly kept to 2.5V, then the constant voltage is kept to 2.5V until the current is less than 0.02C, the current is changed to 1.0CC/1.0CD after 2 circles, and the power is continuously circulated for 50 circles and then taken down.
The hard carbon materials of examples 1 to 8 and the hard carbon materials of comparative examples 1 to 2 were respectively assembled into 2032 electricity-blocking materials according to the above-described preparation methods, and the electrochemical properties thereof were tested, and the results are shown in table 1.
TABLE 1
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the hard carbon material is characterized by comprising the following steps:
s1, pretreating a mixture of terpene resin, graphene oxide and a cross-linking agent to obtain a hard carbon precursor;
s2, performing high-temperature carbonization treatment on the mixture of the hard carbon precursor and the pore-forming agent to obtain the hard carbon material.
2. The method for producing hard carbon according to claim 1, wherein in step S1, the terpene resin has a softening point of 50 to 140 ℃ and a carbon residue ratio of 5 to 12%;
preferably, the number of layers of the graphene oxide is 1-5, and the sheet diameter is equal to that of the graphene oxide<20 μm, oxygen content<30wt％，I D /I G >0.8；
Preferably, the crosslinking agent includes at least one of monoammonium phosphate, phosphorus pentoxide, dopamine, thiourea and maleic anhydride.
3. The method according to claim 1, wherein in step S1, the mass ratio of the terpene resin, the graphene oxide, and the crosslinking agent is (2 to 6): (0.5-1.5): (0.5-1.5).
4. The method for producing a hard carbon material according to claim 1, wherein in step S1, the method further comprises grinding before the pretreatment;
preferably, the milling comprises ball milling;
preferably, the grinding speed is 100-800 rmp, and the grinding time is 1-3 h.
5. The method for producing a hard carbon material according to claim 1, wherein in step S1, the pretreatment includes: heating to 280-410 ℃ under inert atmosphere, preserving heat for 0.5-4 h, and cooling;
preferably, the heating rate is 1-10 ℃/min.
6. The method for producing a hard carbon material according to claim 1, wherein in step S2, the pore-forming agent comprises KOH, naOH, C 2 H 5 ONa and C 2 H 5 At least one of OK;
preferably, the mass ratio of the hard carbon precursor to the pore-forming agent is (3-8): 1.
7. the method for producing a hard carbon material according to claim 1, wherein in step S2, the method further comprises grinding before the high-temperature carbonization treatment;
preferably, the milling comprises ball milling;
preferably, the grinding speed is 200-1500 rmp, and the grinding time is 1-3 h.
8. The method of producing a hard carbon material according to claim 1, wherein in step S2, the high-temperature carbonization includes: heating to 1300-1600 ℃ under inert atmosphere, and preserving heat for 2-12 h;
preferably, the heating rate is 3-15 ℃/min.
9. A hard carbon material characterized by being produced by the method for producing a hard carbon material according to any one of claims 1 to 8.
10. A negative electrode sheet comprising the hard carbon material of claim 9.
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