CN118213510A - Iron-based porous carbon sodium ion battery composite anode material and preparation method thereof - Google Patents
Iron-based porous carbon sodium ion battery composite anode material and preparation method thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 370
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 181
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 239000010405 anode material Substances 0.000 title claims abstract description 41
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 36
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 claims abstract description 66
- 238000005245 sintering Methods 0.000 claims abstract description 43
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052960 marcasite Inorganic materials 0.000 claims abstract description 6
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 6
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 63
- 239000012159 carrier gas Substances 0.000 claims description 49
- 238000000151 deposition Methods 0.000 claims description 46
- 230000008021 deposition Effects 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 125000005842 heteroatom Chemical group 0.000 claims description 22
- 239000002296 pyrolytic carbon Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 6
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 229960000225 ferrous fumarate Drugs 0.000 claims description 6
- 235000002332 ferrous fumarate Nutrition 0.000 claims description 6
- 239000011773 ferrous fumarate Substances 0.000 claims description 6
- 229960002413 ferric citrate Drugs 0.000 claims description 5
- 229960001645 ferrous gluconate Drugs 0.000 claims description 5
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 5
- 239000004222 ferrous gluconate Substances 0.000 claims description 5
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 5
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 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 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- -1 vinyl carbon Chemical compound 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an iron-based porous carbon sodium ion battery composite anode material and a preparation method thereof, wherein the composite anode material comprises a porous carbon skeleton, iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are one or more than two of Fe 2O3、Fe3O4、FeS2、FeS、FeSe2 and FeP; the preparation method comprises the following steps: s1, preparing an iron-based@hard carbon composite material, S2, preparing a surface-coated iron-based@hard carbon composite material, and S3, sintering at a high temperature. The iron-based porous carbon sodium ion battery composite anode material and the preparation method thereof have the characteristics of good uniformity, high specific capacity and long cycle life.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to an iron-based porous carbon sodium ion battery composite anode material and a preparation method thereof.
Background
Sodium ion batteries have been rapidly industrialized in recent years as a low cost alternative to lithium ion batteries due to the advantages of abundant resources. The negative electrode plays a decisive role in the performances of energy density, circulation and the like of the sodium ion battery system. Among the numerous sodium storage anode materials, the hard carbon anode has lower cost and better cycle performance, has extremely strong application potential, and the characteristic of lower specific capacity limits the further improvement of the energy density of the sodium ion battery.
In contrast, iron-based negative electrode materials) have higher specific capacity, rich raw materials and low cost, but the materials have poor electronic conductivity and serious volume expansion process in the sodium treatment process, so that the materials are easy to pulverize and agglomerate in the circulation process, and the circulation performance and the rate capability are poor.
In addition, pulverization of the material particles results in unstable electrode/electrolyte interfaces formed, repeated formation and destruction of Solid Electrolyte (SEI) on the electrode surface results in sustained loss of active sodium, further attenuation of capacity. .
Disclosure of Invention
The invention aims to provide an iron-based porous carbon sodium ion battery composite anode material and a preparation method thereof, and the iron-based porous carbon sodium ion battery composite anode material has the characteristics of good uniformity, high specific capacity and long cycle life.
The invention can be realized by the following technical scheme:
the invention discloses an iron-based porous carbon sodium ion battery composite anode material which comprises a porous carbon skeleton, wherein iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are one or more than two of Fe 2O3、Fe3O4、FeS2、FeS、FeSe2 and FeP. In the invention, the reserved buffer space can buffer the volume change of the iron-based nano particles in the charge and discharge process, so that the structural stability is ensured.
Further, the iron-based nano particles are compounded on the porous carbon skeleton in a filling mode, the particle size of the iron-based nano particles is 0.8-45 nm, and the iron-based nano particles of the nano particles are filled in micropores or mesopores in the porous carbon skeleton.
Further, the iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces.
Further, in the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2g-1.
The invention also provides a preparation method for protecting the iron-based porous carbon sodium ion battery composite anode material, which comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
In the preparation process of the iron-based@hard carbon composite material in the step S1, carrier gas is brought into a pyrolytic iron source to a porous carbon area, and the pyrolytic iron source is adsorbed in pores of the porous carbon and is decomposed to form ferric oxide under the catalysis of pore walls; when the heteroatom-containing gas is present, the pyrolyzed iron source is deposited with its high temperature reaction to form iron-based nanoparticles such as iron sulfide, iron phosphide, and iron selenide. The preparation conditions of this step affect the deposition effect of the iron-based nanoparticles. Specifically, increasing the deposition temperature and extending the deposition time increases the deposition amount of the iron-based material. The deposition temperature is too low, so that longer deposition time is needed, and the production cost is increased; the deposition temperature is too high, and a pyrolytic iron source is easy to decompose and deposit on the surface of the porous carbon substrate and cannot deposit in the pores, so that the aim of the invention is not achieved. Too low a deposition amount can affect the specific capacity of the composite material, and too high a deposition amount can cause the lack of pores in the composite material, so that the purpose of buffering the volume expansion of the iron-based material can not be achieved. Comprehensive consideration of preparation conditions is required to ensure that the degree of filling of the porous carbon pores is at a proper level.
In the preparation process of the surface coated iron-based@hard carbon composite material in the step S2, the preparation conditions influence the coating effect of the carbon layer. In particular, higher deposition temperatures and longer deposition times increase the coating amount of the carbon layer. The deposition amount is too high, the specific capacity of the composite material is reduced, and the coating layer is too thin, so that a complete coating layer cannot be formed, and the aim of isolating the iron-based nano particles from being contacted with electrolyte is not achieved.
In the high-temperature sintering process of step S3, the purpose of high-temperature sintering is to graphitize the coated carbon layer, improve the density of the carbon layer, reduce the porosity, and simultaneously combine the coated carbon layer with the carbon atoms in the base material more tightly at Wen Chongpai. The sintering temperature cannot be higher than the boiling point of the iron-based material.
Further, in step S1, the carrier gas is nitrogen and/or argon, the flow rate of the carrier gas is 20-300 Sccm, the deposition temperature is 300-800 ℃, and the deposition time is 0.2-3 h; the heteroatom-containing gas is one or more than two of H 2S、PH3、H2 Se.
Further, in step S1, the source of pyrolytic iron is one or more of ferrocene, iron phthalocyanine, ferrous gluconate, ferrous fumarate, and ferric citrate.
Further, in step S2, the carrier gas is nitrogen and/or argon, the carrier gas flow rate is 20-300 Sccm, the deposition temperature is 400-1000 ℃, and the deposition time is 0.2-1 h.
Further, in step S2, the pyrolytic carbon source is one or more of benzene, toluene, trimethylbenzene, acetylene, ethanol, formaldehyde, thiophene, pyridine and/or thioether.
Further, in step S3, the conditions for high temperature sintering are: the temperature rising rate is 0.5-10 ℃/min, the sintering temperature is 500-1600 ℃, and the sintering time is 1-5 h.
The iron-based porous carbon sodium ion battery composite anode material and the preparation method thereof have the following beneficial effects:
In the negative electrode material, the porous carbon skeleton is used as a substrate, and the carbon material is used as a buffer substrate material, so that particle aggregation can be inhibited, volume expansion is relieved, a conductive network is provided, and the basic characteristic of long-cycle stability of the hard carbon material is fully exerted; the advantage of high specific capacity of the composite iron-based nano particles is brought into play by compounding the iron-based nano particles; by coating the hard carbon layer, the specific surface area of the porous carbon is reduced, the irreversible decomposition of the electrolyte is inhibited, and the first-week coulomb efficiency of the hard carbon material is improved. .
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
The invention discloses an iron-based porous carbon sodium ion battery composite anode material which comprises a porous carbon skeleton, wherein iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are one or more than two of Fe 2O3、Fe3O4、FeS2、FeS、FeSe2 and FeP.
Further, the iron-based nano particles are compounded on the porous carbon skeleton in a filling mode, the particle size of the iron-based nano particles is 0.8-45 nm, and the iron-based nano particles of the nano particles are filled in micropores or mesopores in the porous carbon skeleton.
Further, the iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces.
Further, in the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2g-1.
The invention also provides a preparation method for protecting the iron-based porous carbon sodium ion battery composite anode material, which comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
Further, in step S1, the carrier gas is nitrogen and/or argon, the flow rate of the carrier gas is 20-300 Sccm, the deposition temperature is 300-800 ℃, and the deposition time is 0.2-3 h; the heteroatom-containing gas is one or more than two of H 2S、PH3、H2 Se.
Further, in step S1, the source of pyrolytic iron is one or more of ferrocene, iron phthalocyanine, ferrous gluconate, ferrous fumarate, and ferric citrate.
Further, in step S2, the carrier gas is nitrogen and/or argon, the carrier gas flow rate is 20-300 Sccm, the deposition temperature is 400-1000 ℃, and the deposition time is 0.2-1 h.
Further, in step S2, the pyrolytic carbon source is one or more of benzene, toluene, trimethylbenzene, acetylene, ethanol, formaldehyde, thiophene, pyridine and/or thioether.
Further, in step S3, the conditions for high temperature sintering are: the temperature rising rate is 0.5-10 ℃/min, the sintering temperature is 500-1600 ℃, and the sintering time is 1-5 h.
Example 1
The embodiment relates to an iron-based porous carbon sodium ion battery composite anode material, and a preparation method thereof comprises the following steps:
s1, preparing an iron-based @ hard carbon composite material: and (3) processing by using a chemical vapor deposition system, and adjusting the gas circuit of the chemical vapor deposition system to enable the gas circuit of the iron source to be connected into the system. The porous carbon had an average pore diameter of 2.5 nm and a specific surface area of 1800 m 2/g. Placing a porous carbon substrate material into a tubular furnace, wherein an iron source is ferrocene, nitrogen is introduced as carrier gas, the flow rate of the carrier gas is 100 Sccm, the deposition temperature is 500 ℃, the deposition time is 2.5 h, and the Fe 2O3 @hard carbon composite material is obtained.
S2, chemical vapor deposition: switching a vapor deposition gas path, heating the porous carbon substrate area to 450 ℃, introducing nitrogen into the porous carbon substrate area, introducing a vinyl carbon source, wherein the flow rate of carrier gas nitrogen is 100 Sccm, and the deposition time is 30min, so as to obtain the surface-coated iron-based @ hard carbon composite material.
S3, sintering at a high temperature: and (3) sintering the surface-coated iron-based@hard carbon composite material obtained in the step (S2) at a high temperature, heating to 1300: 1300 o ℃ in a nitrogen gas atmosphere at a heating rate of 2 o C/min, and preserving heat to 2: 2h to obtain the final negative electrode material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the hard carbon material, super P, CMC and SBR were mixed to be homogenized in a mass ratio of 94:1.5:2:2.5, a black paste was coated on a copper foil using a 120 um four-sided fabricator, and then the film was dried in a vacuum oven at 100℃for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO 4 EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
The first week reversible specific capacities of the iron-based composite electrodes in example 1 were 377 mAh/g, respectively, showing higher sodium storage capacities. The capacity of the iron-based composite electrode in example 1 is maintained to be up to 85% after 1000 weeks of circulation, and the iron-based composite electrode shows better circulation stability. Example 1 the reason for the high cycle stability is on the one hand that the iron-based nano-iron-based nanoparticles are small in size, the sodium treatment process has limited volume expansion, and the hard carbon base material serves as an electron transport network to transport electrons and can buffer the volume expansion of the alloy iron-based nanoparticles; the other is that the surface coated carbon layer effectively isolates the alloy from contacting with electrolyte, thus improving the cycling stability of the electrode/interface.
Example 2
The embodiment relates to an iron-based porous carbon sodium ion battery composite anode material, and a preparation method thereof comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: and (3) processing by using a chemical vapor deposition system, and adjusting the gas circuit of the chemical vapor deposition system to enable the gas circuit of the iron source to be connected into the system. The porous carbon had an average pore diameter of 2.5 nm and a specific surface area of 1800 m 2/g. Placing a porous carbon substrate material into a tube furnace, wherein an iron source is ferrocene, nitrogen is introduced as carrier gas, the flow rate of the carrier gas is 100 Sccm, meanwhile, hydrogen sulfide gas is introduced, the deposition temperature is 500 ℃, and the deposition time is 2 h, so that the FeS@hard carbon composite material is obtained.
S2, chemical vapor deposition: switching a vapor deposition gas path, heating the porous carbon substrate area to 450 ℃, introducing nitrogen into the porous carbon substrate area, introducing a vinyl carbon source, wherein the flow rate of carrier gas nitrogen is 100 Sccm, and the deposition time is 30min, so as to obtain the FeS@hard carbon composite material with the surface coated.
S3, sintering at a high temperature: and (3) sintering the FeS@hard carbon composite material coated with the surface obtained in the step (S2) at a high temperature, heating to 1300: 1300 o ℃ in a nitrogen gas atmosphere at a heating rate of 2 o C/min, and preserving heat to 2: 2h to obtain the final negative electrode material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the hard carbon material, super P, CMC and SBR were mixed to be homogenized in a mass ratio of 94:1.5:2:2.5, a black paste was coated on a copper foil using a 120 um four-sided fabricator, and then the film was dried in a vacuum oven at 100℃for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO 4 EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
The first week reversible specific capacities of the iron-based composite electrodes in example 2 were 402 mAh/g, respectively, showing higher sodium storage capacities. The capacity of the iron-based composite electrode in example 2 is kept to be 83.2% after 1000 weeks of circulation, and the iron-based composite electrode shows better circulation stability.
Example 3
The embodiment discloses an iron-based porous carbon sodium ion battery composite anode material, which comprises a porous carbon skeleton, wherein iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are Fe 2O3、Fe3O4.
In this embodiment, the manner of compositing the iron-based nanoparticles on the porous carbon skeleton is filling, the particle size of the iron-based nanoparticles is 0.8-45 nm, and the iron-based nanoparticles of the nanoparticles are filled in micropores or mesopores inside the porous carbon skeleton. The iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces. In the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2g-1.
The preparation method of the iron-based porous carbon sodium ion battery composite anode material comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
In this embodiment, in step S1, the carrier gas is inert gas, the inert gas is nitrogen, the carrier gas flow rate is 300 Sccm, the deposition temperature is 600 ℃, and the deposition time is 0.2 h; the heteroatom-containing gas is H 2 S; the pyrolytic iron source is ferrocene and iron phthalocyanine.
In this embodiment, in step S2, the carrier gas is nitrogen, the carrier gas flow rate is 300 Sccm, the deposition temperature is 700 ℃, and the deposition time is 0.2 h; the pyrolytic carbon source is benzene and toluene.
In this embodiment, in step S3, the conditions for high temperature sintering are: the temperature rising rate is 10 ℃/min, the sintering temperature is 1100 ℃, and the sintering time is 1 h.
Example 4
The embodiment discloses an iron-based porous carbon sodium ion battery composite anode material, which comprises a porous carbon skeleton, wherein iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are Fe 2O3、FeSe2.
In this embodiment, the manner of compositing the iron-based nanoparticles on the porous carbon skeleton is filling, the particle size of the iron-based nanoparticles is 0.8-45 nm, and the iron-based nanoparticles of the nanoparticles are filled in micropores or mesopores inside the porous carbon skeleton. The iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces. In the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2g-1.
The preparation method of the iron-based porous carbon sodium ion battery composite anode material comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
In this embodiment, in step S1, the carrier gas is argon, the carrier gas flow rate is 150 Sccm, the deposition temperature is 300 ℃, and the deposition time is 3 h; the heteroatom-containing gas is H 2 Se; the pyrolytic iron source is ferrous fumarate and ferric citrate.
In this embodiment, in step S2, the carrier gas is argon, the carrier gas flow rate is 200 Sccm, the deposition temperature is 400 ℃, and the deposition time is 1 h; the pyrolytic carbon source is trimethylbenzene and acetylene.
In this embodiment, in step S3, the conditions for high temperature sintering are: the temperature rising rate is 8 ℃/min, the sintering temperature is 500 ℃, and the sintering time is 5 h.
Example 5
The embodiment discloses an iron-based porous carbon sodium ion battery composite anode material, which comprises a porous carbon skeleton, wherein iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are Fe 2O3、Fe3O4、FeS2、FeS、FeSe2 and FeP.
The preparation method of the iron-based porous carbon sodium ion battery composite anode material comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
In this embodiment, in step S1, the carrier gas is nitrogen and/or argon, the carrier gas flow rate is 20-300 Sccm, the deposition temperature is 300-800 ℃, and the deposition time is 0.2-3 h; the heteroatom-containing gas is one or more than two of H 2S、PH3、H2 Se; the pyrolytic iron source is one or more of ferrocene, iron phthalocyanine, ferrous gluconate, ferrous fumarate and ferric citrate.
In this embodiment, in step S2, the carrier gas is nitrogen and argon, the carrier gas flow rate is 20 Sccm, the deposition temperature is 1000 ℃, and the deposition time is 0.5 h; the pyrolytic carbon source is benzene, toluene, trimethylbenzene, acetylene, ethanol and formaldehyde.
In this embodiment, in step S3, the conditions for high temperature sintering are: the temperature rising rate is 0.5 ℃/min, the sintering temperature is 1600 ℃, and the sintering time is 3 h.
Example 6
The embodiment discloses an iron-based porous carbon sodium ion battery composite anode material, which comprises a porous carbon skeleton, wherein iron-based nano particles are compounded in the porous carbon skeleton, a hard carbon layer is coated outside the porous carbon skeleton, and the iron-based nano particles are Fe 2O3、Fe3O4、FeS2、FeS、FeSe2 and FeP.
In this embodiment, the manner of compositing the iron-based nanoparticles on the porous carbon skeleton is filling, the particle size of the iron-based nanoparticles is 0.8-45 nm, and the iron-based nanoparticles of the nanoparticles are filled in micropores or mesopores inside the porous carbon skeleton. The iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces. In the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2g-1.
In this embodiment, the manner of compositing the iron-based nanoparticles on the porous carbon skeleton is filling, the particle size of the iron-based nanoparticles is 0.8-45 nm, and the iron-based nanoparticles of the nanoparticles are filled in micropores or mesopores inside the porous carbon skeleton. The iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces. In the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2g-1.
The preparation method of the iron-based porous carbon sodium ion battery composite anode material comprises the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
In this embodiment, in step S1, the carrier gas is nitrogen and argon, the carrier gas flow rate is 20-300 Sccm, the deposition temperature is 500 ℃, and the deposition time is 2 h; the heteroatom-containing gas is H 2S、PH3、H2 Se; the pyrolytic iron source is ferrocene, iron phthalocyanine, ferrous gluconate, ferrous fumarate.
In this embodiment, in step S2, the carrier gas is nitrogen and argon, the carrier gas flow rate is 100 Sccm, the deposition temperature is 600 ℃, and the deposition time is 0.6 h; the pyrolytic carbon source is benzene, trimethylbenzene, acetylene, ethanol, formaldehyde, thiophene and pyridine.
In this embodiment, in step S3, the conditions for high temperature sintering are: the temperature rising rate is 5 ℃/min, the sintering temperature is 1000 ℃, and the sintering time is 4h.
The foregoing examples are merely exemplary embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.
Claims (10)
1. An iron-based porous carbon sodium ion battery composite anode material comprises a porous carbon skeleton, and is characterized in that: the porous carbon skeleton is internally compounded with iron-based nano particles, the porous carbon skeleton is externally coated with a hard carbon layer, and the iron-based nano particles are one or more than two of Fe 2O3、Fe3O4、FeS2、FeS、FeSe2 and FeP.
2. The iron-based porous carbon sodium ion battery composite anode material according to claim 1, wherein: the method for compositing the iron-based nano particles on the porous carbon skeleton is filling, the particle size of the iron-based nano particles is 0.8-45 nm, and the iron-based nano particles of the nano particles are filled in micropores or mesopores in the porous carbon skeleton.
3. The iron-based porous carbon sodium ion battery composite anode material according to claim 2, wherein: the iron-based nano particles account for 60-90% of the total pore volume of the porous carbon, and the rest unfilled pores are reserved buffer spaces.
4. The iron-based porous carbon sodium ion battery composite anode material according to claim 3, wherein: in the porous carbon skeleton, the average pore diameter of mesopores or micropores is 0.8-50 nm, the porosity is 30-60%, and the specific surface area is 1000-3000 m 2 g-1.
5. The method for preparing the iron-based porous carbon sodium ion battery composite anode material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
S1, preparing an iron-based @ hard carbon composite material: treating by using a chemical vapor deposition system, heating a porous carbon substrate area, introducing carrier gas and heteroatom-containing gas into a pyrolyzed iron source to deposit the porous carbon, and performing pyrolysis on the iron source and the heteroatom-containing gas in the pores of the carbon substrate to form iron-based nano particles, thereby obtaining an iron-based@hard carbon composite material;
S2, preparing a surface-coated iron-based @ hard carbon composite material: switching gas paths of a vapor deposition system, heating or cooling to enable a porous carbon substrate area, introducing carrier gas to bring a pyrolytic carbon source into the porous carbon substrate area to enable the pyrolytic carbon source to deposit on the surface of the iron-based @ hard carbon composite material, and obtaining the iron-based @ hard carbon composite material with the surface coated;
S3, sintering at a high temperature: and (3) carrying out high-temperature sintering on the surface-coated iron-based@hard carbon composite material obtained in the step (S2) to obtain a final anode material.
6. The method for preparing the iron-based porous carbon sodium ion battery composite anode material according to claim 5, which is characterized in that: in the step S1, the carrier gas is nitrogen and/or argon, the flow rate of the carrier gas is 20-300 Sccm, the deposition temperature is 300-800 ℃, and the deposition time is 0.2-3 h; the heteroatom-containing gas is one or more than two of H 2S、PH3、H2 Se.
7. The iron-based porous carbon sodium ion battery composite anode material according to claim 5, wherein: in the step S1, the pyrolytic iron source is one or more than two of ferrocene, iron phthalocyanine, ferrous gluconate, ferrous fumarate and ferric citrate.
8. The iron-based porous carbon sodium ion battery composite anode material according to claim 5, wherein: in step S2, the carrier gas is nitrogen and/or argon, the flow rate of the carrier gas is 20-300 Sccm, the deposition temperature is 400-1000 ℃, and the deposition time is 0.2-1 h.
9. The iron-based porous carbon sodium ion battery composite anode material according to claim 5, wherein: in step S2, the pyrolytic carbon source is one or more of benzene, toluene, trimethylbenzene, acetylene, ethanol, formaldehyde, thiophene, pyridine and/or thioether.
10. The iron-based porous carbon sodium ion battery composite anode material according to claim 5, wherein: in step S3, the conditions for high temperature sintering are: the temperature rising rate is 0.5-10 ℃/min, the sintering temperature is 500-1600 ℃, and the sintering time is 1-5 h.
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