CN115321514A - Hard carbon material and preparation method and application thereof - Google Patents
Hard carbon material and preparation method and application thereof Download PDFInfo
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- CN115321514A CN115321514A CN202211042344.XA CN202211042344A CN115321514A CN 115321514 A CN115321514 A CN 115321514A CN 202211042344 A CN202211042344 A CN 202211042344A CN 115321514 A CN115321514 A CN 115321514A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 125
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 14
- 125000004429 atom Chemical group 0.000 claims description 36
- 239000007833 carbon precursor Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 23
- 229940000489 arsenate Drugs 0.000 claims description 23
- ZBIBSMMVRNDSNI-UHFFFAOYSA-N diazanium;selenate Chemical compound [NH4+].[NH4+].[O-][Se]([O-])(=O)=O ZBIBSMMVRNDSNI-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000008247 solid mixture Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 229920002101 Chitin Polymers 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- DRGYXGZFRXFMHF-UHFFFAOYSA-N diazanium;tellurate Chemical compound [NH4+].[NH4+].[O-][Te]([O-])(=O)=O DRGYXGZFRXFMHF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052714 tellurium Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005245 sintering Methods 0.000 claims 1
- 239000011229 interlayer Substances 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 239000011669 selenium Substances 0.000 description 21
- 229910052711 selenium Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XPVHUBFHKQQSDA-UHFFFAOYSA-N ammonium arsenate Chemical compound [NH4+].[NH4+].O[As]([O-])([O-])=O XPVHUBFHKQQSDA-UHFFFAOYSA-N 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical group O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention provides a hard carbon material and a preparation method and application thereof. The hard carbon material can be prepared by a simple synthesis process, is doped with at least three heteroatoms, and can increase the interlayer spacing of the hard carbon material and introduce defect sites through the synergistic effect among the heteroatoms, so that the structure of the hard carbon material is greatly distorted, the intercalation capacity and the adsorption capacity of sodium ions are increased, and the hard carbon material has high gram capacity and high rate capability.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a hard carbon material, and a preparation method and application thereof.
Background
The development of energy storage technology puts higher requirements on the performance of lithium ion batteries, and the development of high-performance negative electrode materials becomes one of important research directions for the development of lithium batteries. Because the lithium ion battery has the defects of limited lithium resources and high cost, the research on the sodium ion battery with rich resource reserves and lower cost is also an important research direction of the energy storage technology. The hard carbon has the characteristics of stable structure, long cycle life, good safety performance, high capacity, high multiplying power and the like, and has potential application value in the negative electrodes of lithium ion and sodium ion batteries.
The microstructure of the hard carbon is formed by stacking bent graphite-like sheets to form short-range ordered micro-regions, and simultaneously, random and disordered stacking of each micro-region leaves more nano holes and Na + Can be through defect absorption, inlay between the layer to and in modes such as nanopore packing are stored to hard carbon, consequently the microstructure of hard carbon will directly influence the sodium storage ability, and there are two kinds of main thinking of regulation and control hard carbon microstructure, firstly regulate and control the carbonization process, including carbonization temperature, alternating temperature rate, carbonization mode etc. secondly introduce doping atom and can effectively change the interlamellar spacing of material, surface wettability, electron conductivity to change and store up the sodium performance.
Currently, hard carbon doped atoms mainly have single elements such as N, P and S doped to improve the specific surface area and interlayer spacing of the material, for example, CN 109301220A discloses a nitrogen doped hard carbon material, a preparation method thereof and a potassium ion battery using the same as a negative electrode, wherein the preparation method comprises the following steps: pickling plant resources, and then soaking the plant resources in a nitrogen source aqueous solution to prepare a pre-product; carrying out heat treatment on the pre-product in a protective atmosphere to prepare a nitrogen-doped hard carbon material; the N doping can introduce defects to improve the electronic conductance so as to improve the specific capacity, the single element doping is generally applied, but the content of heteroatoms after activation can be reduced, and the improvement on the distortion and the performance of a hard carbon structure is limited.
Based on the above research, it is necessary to provide a hard carbon material, which can increase the intercalation amount of sodium ions and greatly improve the electrochemical properties such as gram capacity and rate capability of the material.
Disclosure of Invention
The invention aims to provide a hard carbon material and a preparation method and application thereof, the hard carbon material can be doped with at least three kinds of heteroatoms through a simple synthesis process, and through the synergistic action among the heteroatoms, the interlayer spacing can be increased, defect sites can be introduced, and the intercalation capacity and the adsorption capacity of sodium ions are increased, so that the hard carbon material has high gram capacity and high rate capability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing a hard carbon material doped with heteroatoms, the heteroatoms comprising N atoms and M atoms, the M atoms comprising a combination of at least two of As, se, sb or Te.
The hard carbon material is doped with at least three kinds of heteroatoms, and different heteroatoms can play a synergistic effect, so that the performance of the hard carbon material is greatly improved; the doping of the non-metallic nitrogen atoms can not only increase the interlayer spacing of the hard carbon material and cause defect sites, but also change the original electron cloud density distribution of carbon lattices, thereby improving the electronic conductivity, the surface wettability and the ion embedding amount of the hard carbon material, and simultaneously, the sites introduced by the nitrogen doping can promote the M element to be doped into the hard carbon material structure; on the basis of N element doping, at least two elements M can cause larger distortion of the hard carbon material structure by doping, and the interlayer spacing and the disorder degree are further increased, so that C-M bonds with higher bond energy are formed in the hard carbon material, and the electrochemical performance of the hard carbon material is greatly improved; in addition, different atoms doped at the same time have different atom reactivities and different atom radiuses, and bond energy of bonds formed by the atoms and carbon atoms is different, so that different M atoms can be inserted into different positions of the hard carbon material structure, and the problems of nonuniform doping and incapability of ensuring the doping amount are solved.
The M atoms include a combination of at least two of As, se, sb, or Te, and typical, but non-limiting, combinations include a combination of As and Se, a combination of As and Te, a combination of Sb and Se, or a combination of Sb and Te, preferably a combination of As and Se.
Preferably, the heteroatoms include N atoms, as atoms and Se atoms.
The N atom, the As atom and the Se atom can better play a synergistic effect among the hetero atoms, so that the hard carbon material can store more Na ions, and simultaneously promote the rapid diffusion dynamics of the Na ions, although Te and Sb can further improve the interlayer spacing, the interlayer spacing is greatly improved, when the interlayer spacing is far larger than the radius of the sodium ions, the rate capability cannot be further improved, and the compaction density and the volume energy density are reduced, namely the N/As/Se co-doped hard carbon material has high gram capacity and excellent rate capability.
In a second aspect, the present invention provides a method for preparing a hard carbon material according to the first aspect, the method comprising the steps of:
(1) Carrying out hydrothermal reaction on a solution containing a carbon source to obtain a hard carbon precursor;
(2) Mixing the hard carbon precursor in the step (1) with an ammonium salt solution of M to obtain a mixed solution, and drying the mixed solution to obtain a solid mixture;
(3) Calcining the solid mixture of step (2) to obtain the hard carbon material.
The hard carbon material has a simple preparation method even if various heteroatoms are doped, and only the hard carbon precursor and the doping source are mixed and calcined; the method has the advantages that the ammonium salt of M is used as a doping source, so that the doping source of M atoms can be provided, ammonium ions can be used as a nitrogen source, the step of doping various atoms is simplified into one step, the nitrogen source and a hard carbon precursor are not required to be additionally provided for doping, the preparation process for simultaneously doping different elements is greatly simplified, various heteroatoms are simultaneously doped, the doping uniformity is improved, and the performance of a hard carbon material is further improved.
Preferably, the carbon source in step (1) comprises any one or a combination of at least two of chitin, starch, cellulose or chitosan, and typical but non-limiting combinations comprise a combination of chitin and starch, or a combination of cellulose and chitosan, preferably chitin.
The carbon source is preferably chitin, and when the chitin is used as a hard carbon precursor after hydrothermal treatment, the carbon source has the advantages of larger porosity, large interlayer spacing, easy doping of heteroatoms and higher gram volume and rate capability.
Preferably, the concentration of the carbon source in the solution comprising the carbon source in step (1) is 1.1 to 2g/mL, and may be, for example, 1.1g/mL, 1.2g/mL, 1.3g/mL, 1.4g/mL, 1.5g/mL, 1.6g/mL, 1.7g/mL, 1.8g/mL, 1.9g/mL, or 2g/mL, but is not limited to the recited values, and specifically non-recited values within the range of values are equally applicable.
Preferably, the hydrothermal reaction in step (1) is carried out at a temperature of 150 to 230 ℃, for example 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 200 ℃ or 230 ℃ for 5 to 10 hours, for example 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but not limited to the recited values, and any values not recited in the numerical ranges are equally applicable.
Preferably, after the hydrothermal reaction in the step (1) is finished, the method further comprises the step of washing and drying the solid obtained by the reaction with deionized water.
Preferably, the number of washes is 3 to 5, for example 3, 4 or 5, but not limited to the recited values, and any specifically unrecited values within the numerical range are equally applicable.
Preferably, the drying is performed under vacuum conditions.
Preferably, the hydrothermal reaction in step (1) is carried out in an autoclave.
Preferably, the molar ratio of the ammonium salt of M in step (2) to the hard carbon precursor in step (1) is (5-10) to (90-95), and may be, for example, 5.
Preferably, the ammonium salt of M in step (2) includes a combination of at least two of diammonium arsenate, ammonium selenate, ammonium antimonate or ammonium tellurate, and typical, but not limiting, combinations include a combination of diammonium arsenate and ammonium selenate, a combination of diammonium arsenate and ammonium tellurate, a combination of ammonium antimonate and ammonium tellurate, or a combination of ammonium antimonate and ammonium selenate, preferably a combination of diammonium arsenate and ammonium selenate.
Preferably, the molar ratio of the diammonium arsenate, ammonium selenate and the hard carbon precursor in step (1) is (2-5): (3-5): (90-95), and may be, for example, 2.
Preferably, the drying temperature in step (2) is 60-80 ℃, for example 60 ℃, 70 ℃ or 80 ℃, but not limited to the recited values, and any specifically unrecited values within the numerical range are equally applicable.
Preferably, the calcining in step (3) includes heating to a first temperature with a first heating rate, and then heating to a second temperature with a second heating rate.
Preferably, the first temperature increase rate is 2-4 ℃/min, and can be, for example, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, or 4 ℃/min, but is not limited to the recited values, and any values within the range are equally applicable.
Preferably, the first temperature is 600-800 ℃, for example 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, but not limited to the recited values, values within the range of which specifically unrecited values are equally applicable.
Preferably, the holding time at the first temperature is 2 to 8 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, but not limited to the recited values, and the values not specifically recited in the numerical ranges are also applicable.
Preferably, the second heating rate is 3-6 deg.C/min, and can be, for example, 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, 5 deg.C/min, 5.5 deg.C/min, or 6 deg.C/min, but is not limited to the values recited, and values not specifically recited within the ranges are equally applicable.
Preferably, the second temperature is 1200 to 1700 ℃, for example 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃ or 1700 ℃, but not limited to the recited values, and values within the ranges are equally applicable.
Preferably, the holding time at the second temperature is 2 to 8 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, but not limited to the values listed, and values within the range not specifically listed are equally applicable.
Preferably, the calcination of step (3) is carried out under an inert gas.
Preferably, after the calcination in step (3), the temperature is decreased to room temperature at a cooling rate of 2-5 ℃/min, such as 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, or 5 ℃/min, but not limited to the values listed, and any values not specifically listed within the range of values are also applicable.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) Carrying out hydrothermal reaction on a solution of a carbon source with the concentration of 1.1-2g/mL at 150-230 ℃ for 5-10h, washing the obtained solid with deionized water for 3-5 times, and drying under a vacuum condition to obtain a hard carbon precursor;
(2) Mixing the hard carbon precursor in the step (1) with an ammonium salt solution of M to obtain a mixed solution, and drying the mixed solution at 60-80 ℃ to obtain a solid mixture;
the molar ratio of the ammonium salt of M to the hard carbon precursor in the step (1) is (5-10): 90-95), and the ammonium salt of M comprises the combination of at least two of diammonium arsenate, ammonium selenate, ammonium antimonate or ammonium tellurate;
(3) And (3) under inert gas, heating the solid mixture in the step (2) to 600-800 ℃ at a first heating rate of 2-4 ℃/min, preserving heat for 2-8h, heating to 1200-1700 ℃ at a second heating rate of 3-6 ℃/min, preserving heat for 2-8h, and cooling to room temperature at a cooling rate of 2-5 ℃/min to obtain the hard carbon material.
In a third aspect, the present invention provides a sodium ion battery comprising a hard carbon material as described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The hard carbon material is doped with at least three kinds of heteroatoms, and the different heteroatoms can play a synergistic effect, so that the interlayer spacing and the disorder degree of the hard carbon material are increased, defect sites are caused, the original electron cloud density distribution of carbon lattices is changed, and the electrochemical performance of the hard carbon material is greatly improved;
(2) The hard carbon material of the invention also has a simple preparation method even if doped with various heteroatoms, only the hard carbon precursor and the doping source are mixed and calcined, the step of doping various atoms can be simplified into one step, the preparation process of simultaneously doping different elements is greatly simplified, various heteroatoms are simultaneously doped, the doping uniformity is improved, and the performance of the hard carbon material is further improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a hard carbon material, which is doped with N, as and Se atoms, and a preparation method of the hard carbon material comprises the following steps:
(1) Carrying out hydrothermal reaction on a chitin solution with the concentration of 1.5g/mL at 180 ℃ for 8h, washing the obtained solid with deionized water for 4 times, and drying under a vacuum condition to obtain a hard carbon precursor;
(2) Adding the hard carbon precursor into a solution of diammonium arsenate and ammonium selenate to obtain a mixed solution, and drying the mixed solution at 70 ℃ to obtain a solid mixture;
the molar ratio of the diammonium arsenate to the ammonium selenate to the hard carbon precursor in the step (1) is 4;
(3) And (3) under the argon atmosphere, heating the solid mixture obtained in the step (2) to 700 ℃ at a first heating rate of 3 ℃/min, preserving heat for 5h, then heating to 1400 ℃ at a second heating rate of 4 ℃/min, preserving heat for 6h, and then cooling to room temperature at a cooling rate of 3 ℃/min to obtain the hard carbon material.
Example 2
The embodiment provides a hard carbon material, which is doped with N, as and Se atoms, and a preparation method of the hard carbon material comprises the following steps:
(1) Carrying out hydrothermal reaction on a chitin solution with the concentration of 1.1g/mL at 150 ℃ for 10h, washing the obtained solid with deionized water for 5 times, and drying under a vacuum condition to obtain a hard carbon precursor;
(2) Adding the hard carbon precursor into a solution of diammonium arsenate and ammonium selenate to obtain a mixed solution, and drying the mixed solution at 80 ℃ to obtain a solid mixture;
the molar ratio of the diammonium arsenate to the ammonium selenate to the hard carbon precursor in the step (1) is 2;
(3) And (3) under the argon atmosphere, heating the solid mixture in the step (2) to 800 ℃ at a first heating rate of 4 ℃/min, preserving heat for 2h, then heating to 1200 ℃ at a second heating rate of 3 ℃/min, preserving heat for 8h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain the hard carbon material.
Example 3
The embodiment provides a hard carbon material, which is doped with N, as and Se atoms, and a preparation method of the hard carbon material comprises the following steps:
(1) Carrying out hydrothermal reaction on chitin solution with the concentration of 2g/mL at 230 ℃ for 5h, cleaning the obtained solid with deionized water for 3 times, and drying under a vacuum condition to obtain a hard carbon precursor;
(2) Adding the hard carbon precursor into a solution of diammonium arsenate and ammonium selenate to obtain a mixed solution, and drying the mixed solution at 60-80 ℃ to obtain a solid mixture;
the molar ratio of the diammonium arsenate to the ammonium selenate to the hard carbon precursor in the step (1) is 5;
(3) And (3) under the argon atmosphere, heating the solid mixture in the step (2) to 600 ℃ at a first heating rate of 2 ℃/min, preserving heat for 8h, heating to 1700 ℃ at a second heating rate of 6 ℃/min, preserving heat for 2h, and cooling to room temperature at a cooling rate of 2 ℃/min to obtain the hard carbon material.
Example 4
This example provides a hard carbon material doped with N, as and Te atoms, prepared in the same manner As in example 1, except that ammonium selenate in an equimolar amount was replaced with ammonium tellurate in step (2).
Example 5
This example provides a hard carbon material doped with N, sb, and Se atoms, which was prepared in the same manner as in example 1, except that an equimolar amount of diammonium arsenate was substituted for ammonium antimonate in step (2).
Example 6
This example provides a hard carbon material doped with N, sb and Te atoms, prepared by the same method as in example 1, except that an equimolar amount of diammonium arsenate was replaced with ammonium antimonate and an equimolar amount of ammonium selenate was replaced with ammonium tellurate in step (2).
Example 7
This example provides a hard carbon material doped with N, as, sb, and Se atoms, which was prepared in the same manner As in example 1, except that half of the molar amount of diammonium arsenate in step (2) was replaced with ammonium antimonate.
Example 8
This example provides a hard carbon material doped with N, as and Se atoms, which was prepared in the same manner As in example 1, except that the concentrations of chitin and the like in step (1) were replaced with starch.
Example 9
This example provides a hard carbon material doped with N, as, and Se atoms, which was prepared in the same manner As in example 1, except that the chitin etc. concentration in step (1) was replaced with cellulose.
Example 10
This example provides a hard carbon material doped with N, as and Se atoms, prepared by the same method As in example 1 except that the molar ratio of diammonium arsenate, ammonium selenate in step (2) and the hard carbon precursor in step (1) is 1.
Example 11
This example provides a hard carbon material doped with N, as and Se atoms, prepared by the same method As in example 1 except that the molar ratio of diammonium arsenate, ammonium selenate in step (2) and the hard carbon precursor in step (1) is 7.
Comparative example 1
The present comparative example provides a hard carbon material doped with N atoms, the preparation method of the hard carbon material including the steps of:
(1) Carrying out hydrothermal reaction on a chitin solution with the concentration of 1.5g/mL at 180 ℃ for 8h, washing the obtained solid with deionized water for 4 times, and drying under a vacuum condition to obtain a hard carbon precursor;
(2) Adding the hard carbon precursor into a urea solution to obtain a mixed solution, and drying the mixed solution at 70 ℃ to obtain a solid mixture;
the molar ratio of the urea to the hard carbon precursor in the step (1) is 7;
(3) And (3) under the argon atmosphere, heating the solid mixture obtained in the step (2) to 700 ℃ at a first heating rate of 3 ℃/min, preserving heat for 5h, then heating to 1400 ℃ at a second heating rate of 4 ℃/min, preserving heat for 6h, and then cooling to room temperature at a cooling rate of 3 ℃/min to obtain the hard carbon material.
Comparative example 2
This comparative example provides a hard carbon material doped with N and As atoms, which was prepared in the same manner As in example 1, except that ammonium selenate was equimolar-substituted for diammonium arsenate in step (2).
Comparative example 3
This comparative example provides a hard carbon material doped with N and Se atoms, which was prepared in the same manner as in example 1, except that ammonium arsenate was equimolar to ammonium selenate in the step (2).
Comparative example 4
This comparative example provides a hard carbon material doped with As and Se atoms, which was prepared in the same manner As in example 1, except that the diammonium arsenate in step (2) was replaced with equimolar amounts of arsenic oxide and ammonium selenate was replaced with equimolar amounts of selenium oxide.
The hard carbon material, the conductive agent SP and the binder PVDF obtained in the above examples and comparative examples are compounded according to a mass ratio of 93 6 The solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC) is used as electrolyte, fluoroethylene carbonate is used(FEC) as electrolyte additive (molar ratio of FEC and EC + DMC 1: 20), assembling CR2032 battery in hydrogen-filled glove box, performing charge-discharge test with charge-discharge rate of 0.1C (voltage range 0-2V); electrochemical performance was tested on the LAND cell test system of Wuhanjinnuo electronics, 0.1C first effect, 0.1C capacity, cycle performance and rate performance are shown in Table 1:
TABLE 1
From the above table it can be seen that:
(1) The hard carbon material doped with various heteroatoms changes the structure of the hard carbon material, so that the sodium ion battery prepared from the hard carbon material has high gram capacity, first effect and cycle performance, and excellent rate performance; as can be seen from examples 1 and 4 to 6, compared with the N/As/Se co-doped hard carbon material, the N/Sb/Se co-doped hard carbon material, and the N/Sb/Te co-doped hard carbon material, the N, as, and Se can better perform a synergistic effect, and Sb and Te have larger atomic radius than As and Se, so that the metal property is stronger, the interlayer spacing after doping is too large, the interlayer spacing is far larger than the sodium radius, the rate capability is not improved, and the interlayer spacing is too large, the material compaction density is reduced, which is not beneficial to improving the volume energy density; from example 1 and example 7, it can be seen that, under the condition of keeping the same doping amount of the heteroatoms, the doping performance of the four heteroatoms in example 7 is similar to that of the three heteroatoms in example 1, and the doping of the three heteroatoms is preferred on the basis of ensuring the simple preparation process and saving raw materials.
(2) From the embodiment 1 and the embodiments 8-9, the carbon source preferred for preparing the hard carbon material is chitin, and the preparation of the chitin enables the hard carbon material to have higher porosity and higher gram volume, so that hetero atoms are easier to dope, and the electrochemical properties such as rate capability and the like are further improved; as can be seen from example 1 and examples 10 to 11, the doping amount of the present invention can ensure that the hard carbon material has a higher gram capacity and can further improve the electrochemical performance within a reasonable range, and if the doping ratio is too high, the gram capacity is significantly reduced, the rate capability is reduced, the doping ratio is too low, the doping effect cannot be achieved, and the rate capability and the gram capacity are not significantly improved.
(3) As can be seen from the example 1 and the comparative example 1, the structure of the hard carbon material is not greatly distorted by the pure nitrogen atom doping, and the nitrogen atom content is reduced after the hard carbon material is activated, so that the improvement of the material performance is limited; as can be seen from example 1 and comparative examples 2 to 4, the doping of the non-metallic nitrogen atoms and the M atoms is beneficial to the synergistic effect between the heteroatoms, so as to ensure the doping amount of the heteroatoms in the activated hard carbon material, so that the hard carbon material stores more sodium ions, and the diffusion rate of the sodium ions is increased, thereby greatly improving the electrochemical performance of the hard carbon material.
In summary, the invention provides a hard carbon material, a preparation method and an application thereof, the hard carbon material is doped with various heteroatoms, but the preparation method is simple, the obtained hard carbon material has large interlayer spacing, can cause more defect sites, is uniformly doped with the heteroatoms, and can greatly improve the electrochemical performance of the hard carbon material, especially can obviously improve the gram capacity and the rate capability.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A hard carbon material, characterized in that the hard carbon material is doped with heteroatoms, the heteroatoms comprising N atoms and M atoms, the M atoms comprising a combination of at least two of As, se, sb or Te.
2. The hard carbon material of claim 1, wherein the heteroatoms comprise N atoms, as atoms, and Se atoms.
3. A method for preparing a hard carbon material according to claim 1 or 2, comprising the steps of:
(1) Carrying out hydrothermal reaction on a solution containing a carbon source to obtain a hard carbon precursor;
(2) Mixing the hard carbon precursor in the step (1) with an ammonium salt solution of M to obtain a mixed solution, and drying the mixed solution to obtain a solid mixture;
(3) Calcining the solid mixture of step (2) to obtain the hard carbon material.
4. The method according to claim 3, wherein the carbon source in step (1) comprises any one or a combination of at least two of chitin, starch, cellulose or chitosan, preferably chitin;
preferably, the concentration of the carbon source in the solution comprising the carbon source in the step (1) is 1.1-2g/mL;
preferably, the temperature of the hydrothermal reaction in the step (1) is 150-230 ℃ and the time is 5-10h.
5. The preparation method according to claim 3 or 4, characterized in that after the hydrothermal reaction in step (1) is finished, the method further comprises the steps of washing and drying the solid obtained by the reaction with deionized water;
preferably, the number of washing times is 3 to 5;
preferably, the drying is performed under vacuum conditions.
6. The method according to any one of claims 3 to 5, wherein the molar ratio of the ammonium salt of M in step (2) to the hard carbon precursor in step (1) is (5-10): (90-95);
preferably, the ammonium salt of M in step (2) comprises a combination of at least two of diammonium arsenate, ammonium selenate, ammonium antimonate or ammonium tellurate, preferably a combination of diammonium arsenate and ammonium selenate;
preferably, the molar ratio of the diammonium arsenate to the ammonium selenate to the hard carbon precursor in the step (1) is (2-5): (3-5): (90-95);
preferably, the temperature for drying in step (2) is 60-80 ℃.
7. The method according to any one of claims 3 to 6, wherein the calcining in the step (3) comprises raising the temperature to a first temperature at a first temperature raising rate and then raising the temperature to a second temperature at a second temperature raising rate;
preferably, the first heating rate is 2-4 ℃/min;
preferably, the first temperature is 600-800 ℃;
preferably, the holding time of the first temperature is 2-8h.
8. The production method according to claim 7, wherein the second temperature rise rate is 3 to 6 ℃/min;
preferably, the second temperature is 1200-1700 ℃;
preferably, the holding time of the second temperature is 2-8h;
preferably, the calcination of step (3) is carried out under an inert gas;
preferably, after the calcining and sintering in the step (3), the temperature is reduced to the room temperature at the cooling rate of 2-5 ℃/min.
9. The production method according to any one of claims 3 to 8, characterized by comprising the steps of:
(1) Carrying out hydrothermal reaction on a solution with a carbon source concentration of 1.1-2g/mL at 150-230 ℃ for 5-10h, washing the obtained solid with deionized water for 3-5 times, and drying under a vacuum condition to obtain a hard carbon precursor;
(2) Mixing the hard carbon precursor in the step (1) with an ammonium salt solution of M to obtain a mixed solution, and drying the mixed solution at 60-80 ℃ to obtain a solid mixture;
the molar ratio of the ammonium salt of M to the hard carbon precursor in the step (1) is (5-10) to (90-95), and the ammonium salt of M comprises a combination of at least two of diammonium arsenate, ammonium selenate, ammonium antimonate and ammonium tellurate;
(3) And (3) under inert gas, heating the solid mixture in the step (2) to 600-800 ℃ at a first heating rate of 2-4 ℃/min, preserving heat for 2-8h, heating to 1200-1700 ℃ at a second heating rate of 3-6 ℃/min, preserving heat for 2-8h, and cooling to room temperature at a cooling rate of 2-5 ℃/min to obtain the hard carbon material.
10. A sodium-ion battery, characterized in that the sodium-ion battery comprises the hard carbon material according to claim 1 or 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011157013A1 (en) * | 2010-06-18 | 2011-12-22 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same |
| US20140272592A1 (en) * | 2013-03-14 | 2014-09-18 | Energ2 Technologies, Inc. | Composite carbon materials comprising lithium alloying electrochemical modifiers |
| US20150218001A1 (en) * | 2012-08-06 | 2015-08-06 | Technical Institute of Physics and Chemisty of the Chinese Academy of Sciences | Preparation method of heteroatom doped multifunctional carbon quantum dot and application thereof |
| GB201517661D0 (en) * | 2015-10-06 | 2015-11-18 | Faradion Ltd | Process for preparing hard carbon composite materials |
| CN114551870A (en) * | 2021-12-15 | 2022-05-27 | 深圳先进技术研究院 | Hard carbon negative electrode material of sodium ion battery and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011157013A1 (en) * | 2010-06-18 | 2011-12-22 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same |
| US20150218001A1 (en) * | 2012-08-06 | 2015-08-06 | Technical Institute of Physics and Chemisty of the Chinese Academy of Sciences | Preparation method of heteroatom doped multifunctional carbon quantum dot and application thereof |
| US20140272592A1 (en) * | 2013-03-14 | 2014-09-18 | Energ2 Technologies, Inc. | Composite carbon materials comprising lithium alloying electrochemical modifiers |
| GB201517661D0 (en) * | 2015-10-06 | 2015-11-18 | Faradion Ltd | Process for preparing hard carbon composite materials |
| CN114551870A (en) * | 2021-12-15 | 2022-05-27 | 深圳先进技术研究院 | Hard carbon negative electrode material of sodium ion battery and preparation method thereof |
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