CN111540892B - Preparation method of iron-based-carbon composite material with core-shell structure - Google Patents
Preparation method of iron-based-carbon composite material with core-shell structure Download PDFInfo
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- CN111540892B CN111540892B CN202010395414.4A CN202010395414A CN111540892B CN 111540892 B CN111540892 B CN 111540892B CN 202010395414 A CN202010395414 A CN 202010395414A CN 111540892 B CN111540892 B CN 111540892B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 47
- 239000011258 core-shell material Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011630 iodine Substances 0.000 claims abstract description 18
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- -1 phenol compound Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007772 electrode material Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- XQQSWXUDAPLMKD-UHFFFAOYSA-N N,N-dimethylheptadecan-1-amine hydrobromide Chemical compound Br.CCCCCCCCCCCCCCCCCN(C)C XQQSWXUDAPLMKD-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 5
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 5
- 229960001553 phloroglucinol Drugs 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 4
- 229910000339 iron disulfide Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- MAQAUGBCWORAAB-UHFFFAOYSA-N [C+4].[O-2].[Fe+2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Fe+2].[O-2].[O-2] MAQAUGBCWORAAB-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940095991 ferrous disulfide Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of an iron-based-carbon composite material with a core-shell structure, which comprises the steps of taking soluble ferric salt as a raw material, performing ferric salt hydrothermal reaction, tetraethyl silicate hydrolysis and polymer coating, repeating the cycle for 0-3 times, treating with strong alkali, carbonizing, and finally reacting with iodine to obtain the iron-based-carbon composite material with the core-shell structure; the iron-based-carbon composite material is of a micro-nano structure and contains 1-4 layers of core-shell structures; the iron-based-carbon composite material has good electrochemical performance and good application prospect in the field of batteries.
Description
Technical Field
The invention relates to a preparation method of an electrode material, in particular to a preparation method of an iron-based-carbon composite material with a core-shell structure.
Background
The core-shell material has a double-layer or multi-layer structure, and different components are respectively enriched inside and outside the core-shell material, so that the functions of the core and the shell are compounded and complemented, and a novel functional material with the performance different from that of the core or the shell can be prepared. Designing and constructing a nanocomposite material with a core-shell structure is a leading field of material science in recent years. The core-shell structure material can realize the compounding and complementation of core and shell functions, and the design concept of the core-shell structure is introduced into the lithium ion battery material in recent years. The negative electrode material taking iron ions in various valence states as ligands is widely applied, such as iron metal oxide, iron disulfide and the like, but the capacity attenuation of the negative electrode material is obvious along with the charge and discharge.
Patent CN 109148864A discloses a ferrous disulfide composite cathode material and a preparation method thereof; the conductive polymer layer is coated on the surface of the iron disulfide, so that the conductivity of the iron disulfide is improved, the conductive polymer layer has certain toughness, and the volume expansion of the iron disulfide in the charging and discharging processes can be buffered, so that the cycling stability of the battery is obviously improved.
Patent CN 108736000A discloses a method for preparing Fe by thermal decomposition2O3A method for preparing a carbon nanotube composite material. The mixture of ferric nitrate and carbon nanotubes was calcined in a tube furnace in an inert gas. The Fe2O3The carbon nanotube composite material has good cycle life, coulombic efficiency, and relatively high energy density and cycle stability.
However, the iron-based electrode material has poor conductivity, and how to improve the electrochemical performance of the iron-based electrode material still needs to be solved.
Disclosure of Invention
Aiming at the defects of the prior art scheme, the invention aims to provide a preparation method of an iron-based-carbon composite material with a core-shell structure.
The invention relates to a preparation method of an iron-based-carbon composite material with a core-shell structure, which comprises the steps of taking soluble ferric salt as a raw material, performing ferric salt hydrothermal reaction, tetraethyl silicate hydrolysis and polymer coating, repeating the cycle for 0-3 times, treating with strong alkali, carbonizing, and finally reacting with iodine to obtain the iron-based-carbon composite material with the core-shell structure; the soluble ferric salt is one of ferric chloride, ferric bromide, ferric nitrate and ferric acetate; the polymer precursor is phenol compound and aldehyde compound; the phenol compound is one of phenol, m-diphenol, m-triphenol, p-phenol and o-phenol; the aldehyde compound is one of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde; a preparation method of an iron-based-carbon composite material with a core-shell structure comprises the following steps:
1) weighing a certain mass of soluble ferric salt, trisodium citrate and an ethanol/water mixture, mixing, and carrying out hydrothermal reaction at 100-240 ℃ for 3-20 hours; wherein the volume ratio of ethanol to water is 80-100;
2) dispersing the product obtained in the step 1 in an alcohol solvent, adding water and tetraethyl silicate, and stirring for 5-10 hours at the temperature of 20-70 ℃; filtering and washing; wherein the molar ratio of iron to silicon is 2-5;
3) sequentially adding the product in the step 2 into hexadecyltrimethylamine bromide, water, a phenol compound, absolute ethyl alcohol, ammonia water and an aldehyde compound, and stirring for 5-10 hours at the temperature of 20-70 ℃; filtering and washing;
4) adding the product of the step 3 into N2Carbonizing at the temperature of 800 ℃ for 2-10h under the atmosphere of 400-;
5) repeating the product of the step 4 for 0-3 times of cycles of the step 1, the step 2, the step 3 and the step 4;
6) putting the product obtained in the step 5 into a strong alkali solution for 5-10 hours; washing and drying;
7) mixing the product obtained in the step 6 with iodine, and carrying out solid solution at the temperature of 100-200 ℃ for 2-10 hours; then solid solution is carried out for 1-5 hours at the temperature of 400-800 ℃; obtaining the iron-based-carbon composite material with the core-shell structure; wherein the molar ratio of iodine to iron is 0.2-1.2; the iron-based-carbon composite material contains 1-4 layers of core-shell structures;
the iron-based-carbon composite material contains micro-nano structures;
the molar ratio of the iron element to the phenol compound is 0.5-5;
the molar ratio of the phenol compound to the aldehyde compound is 1-1.5.
The iron oxide-carbon with a core-shell structure is designed as a raw material, and the iron-based-carbon composite material with the core-shell structure is prepared through an iodine reaction. Compared with the prior art, the preparation method of the iron-based-carbon composite material with the core-shell structure provided by the invention has the following advantages:
1) the preparation process is simple, the working procedures are controllable, and industrial production can be realized;
2) guiding silicon dioxide to deposit on the surface by taking iron oxide as a template, polymerizing a conductive material on the surface, depositing the iron oxide, removing the silicon dioxide, carbonizing, and reacting with iodine to form a micro-nano core-shell structure; the conductivity of the electrode material is greatly improved;
3) the iron-based-carbon composite material with the micro-nano core-shell structure is beneficial to the intercalation/desorption of lithium ions. The specific capacity and the rate capability of the electrode material are greatly improved; the material has good application prospect in the field of lithium ion batteries.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following embodiments are described in detail as follows:
example 1
A preparation method of an iron-based-carbon composite material with a layer of core-shell structure comprises the following steps:
1) weighing a certain mass of soluble ferric salt, trisodium citrate and an ethanol/water mixture, mixing, and carrying out hydrothermal reaction at 160 ℃ for 10 hours; wherein the volume ratio of ethanol to water is 80;
2) dispersing the product obtained in the step 1 in an alcohol solvent, adding water and tetraethyl silicate, and stirring for 5 hours at 40 ℃; filtering and washing; wherein the molar ratio of iron to silicon is 5;
3) sequentially adding the product in the step 2 into hexadecyltrimethylamine bromide, water, a phenol compound, absolute ethyl alcohol, ammonia water and an aldehyde compound, and stirring for 5 hours at 50 ℃; filtering and washing;
4) adding the product of the step 3 into N2Carbonizing for 5 hours at 600 ℃ in the atmosphere;
5) putting the product obtained in the step 4 into a strong alkali solution for 10 hours; washing and drying;
6) mixing the product obtained in the step 5 with iodine, and performing solid solution at 150 ℃ for 5 hours; then solid dissolving for 2 hours at 500 ℃; obtaining the iron-based-carbon composite material with a layer of core-shell structure.
The component design of the iron-based-carbon composite material with a layer of core-shell structure comprises the following steps:
1)0.1mol of ferric chloride; 0.025mol tetraethyl silicate; 0.25mol of resorcinol; 0.2mol of formaldehyde; 0.06mol of iodine;
2)0.1mol of ferric nitrate; 0.03mol tetraethyl silicate; 0.2mol of phenol; 0.20mol of formaldehyde; 0.08mol of iodine;
microstructure display: the iron-based-carbon composite material has a micro-nano core-shell structure, and the carbon core shell covers the iron-based electrode material; the electrochemical test results show that: the iron-based-carbon composite material has good electrochemical performance.
Example 2
A preparation method of an iron-based-carbon composite material with a two-layer core-shell structure comprises the following steps:
1) weighing a certain mass of soluble ferric salt, trisodium citrate and an ethanol/water mixture, mixing, and carrying out hydrothermal reaction at 180 ℃ for 5 hours; wherein the volume ratio of ethanol to water is 90;
2) dispersing the product obtained in the step 1 in an alcohol solvent, adding water and tetraethyl silicate, and stirring for 5 hours at 40 ℃; filtering and washing; wherein the molar ratio of iron to silicon is 4;
3) sequentially adding the product in the step 2 into hexadecyltrimethylamine bromide, water, a phenol compound, absolute ethyl alcohol, ammonia water and an aldehyde compound, and stirring for 5 hours at 50 ℃; filtering and washing;
4) adding the product of the step 3 into N2Carbonizing for 10h at 500 ℃ in the atmosphere;
5) repeating the cycle of the steps 1,2,3 and 4 for 1 time by using the product obtained in the step 4;
6) putting the product obtained in the step 5) into a strong alkali solution for 10 hours; washing and drying;
7) mixing the product obtained in the step 6 with iodine, and performing solid solution at 200 ℃ for 3 hours; then solid dissolving for 2 hours at 600 ℃; obtaining the iron-based-carbon composite material with a two-layer core-shell structure.
The component design of the iron-based-carbon composite material with the two-layer core-shell structure comprises the following steps:
3) a first layer: 0.025mol ferric chloride; 0.0125mol of tetraethyl silicate; 0.12mol of resorcinol; 0.1mol of formaldehyde; 0.025mol iodine;
a second layer: 0.05mol of ferric chloride; 0.0125mol of tetraethyl silicate; 0.22mol of resorcinol; 0.2mol of formaldehyde; 0.04mol of iodine;
4) a first layer: 0.03mol of ferric bromide; 0.0125mol of tetraethyl silicate; 0.12mol of phloroglucinol; 0.12mol of formaldehyde; 0.02mol of iodine;
a second layer: 0.05mol of ferric bromide; 0.0125mol of tetraethyl silicate; 0.20mol of phloroglucinol; 0.15mol of formaldehyde; 0.04mol of iodine;
microstructure display: the iron-based-carbon composite material has a micro-nano core-shell structure, and the carbon core shell covers the iron-based electrode material; the electrochemical test results show that: the iron-based-carbon composite material has good electrochemical performance.
Example 3
A preparation method of an iron-based-carbon composite material with a three-layer core-shell structure comprises the following steps:
1) weighing a certain mass of soluble ferric salt, trisodium citrate and an ethanol/water mixture, mixing, and carrying out hydrothermal reaction for 4 hours at 200 ℃; wherein the volume ratio of ethanol to water is 85;
2) dispersing the product obtained in the step 1 in an alcohol solvent, adding water and tetraethyl silicate, and stirring for 5 hours at 40 ℃; filtering and washing; wherein the molar ratio of iron to silicon is 2;
3) sequentially adding the product in the step 2 into hexadecyltrimethylamine bromide, water, a phenol compound, absolute ethyl alcohol, ammonia water and an aldehyde compound, and stirring for 5 hours at 50 ℃; filtering and washing;
4) adding the product of the step 3 into N2Carbonizing at 600 ℃ for 5 hours in the atmosphere;
5) repeating the cycle of the steps 1,2,3 and 4 for 2 times by using the product obtained in the step 4;
6) putting the product obtained in the step 5) into a strong alkali solution for 10 hours; washing and drying;
7) mixing the product obtained in the step 6 with iodine, and performing solid solution at 150 ℃ for 5 hours; then solid dissolving for 5 hours at 500 ℃; obtaining the iron-based-carbon composite material with a three-layer core-shell structure.
The component design of the iron-based-carbon composite material with the three-layer core-shell structure comprises the following steps:
5) a first layer: 0.06mol of ferric acetate; 0.03mol tetraethyl silicate; 0.15mol of phloroglucinol; 0.15mol of acetaldehyde; 0.06mol of iodine;
a second layer: 0.06mol of ferric acetate; 0.03mol tetraethyl silicate; 0.2mol of phloroglucinol; 0.2mol of acetaldehyde; 0.06mol of iodine;
and a third layer: 0.06mol of ferric acetate; 0.03mol tetraethyl silicate; 0.25mol of phloroglucinol; 0.25mol of acetaldehyde; 0.06mol of iodine;
6) a first layer: 0.1mol of ferric acetate; 0.04mol of tetraethyl silicate; 0.2mol of p-phenol; 0.16mol of butyraldehyde; 0.1mol of iodine;
a second layer: 0.1mol of ferric acetate; 0.04mol of tetraethyl silicate; 0.25mol of p-phenol; 0.22mol of butyraldehyde; 0.1mol of iodine;
and a third layer: 0.1mol of ferric acetate; 0.04mol of tetraethyl silicate; 0.3mol of p-phenol; 0.28mol of butyraldehyde; 0.1mol of iodine;
microstructure display: the iron-based-carbon composite material has a micro-nano core-shell structure, and the carbon core shell covers the iron-based electrode material; the electrochemical test results show that: the iron-based-carbon composite material has good electrochemical performance.
The above-described embodiments of the patent are intended to be illustrative, but not limiting, of the scope of the patent, which is included for the purpose of better understanding the patent by those skilled in the art; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.
Claims (1)
1. A preparation method of an iron-based-carbon lithium ion battery composite electrode material with a core-shell structure comprises the following steps:
1) weighing a certain mass of soluble ferric salt, trisodium citrate and an ethanol/water mixture, mixing, and carrying out hydrothermal reaction at 100-240 ℃ for 3-20 hours; wherein the soluble ferric salt is one of ferric bromide, ferric nitrate and ferric acetate; the volume ratio of ethanol to water is 80-100;
2) dispersing the product obtained in the step 1) in an alcohol solvent, adding water and tetraethyl silicate, and stirring for 5-10 hours at the temperature of 20-70 ℃; filtering and washing; wherein the molar ratio of iron to silicon is 2-5;
3) sequentially adding the product in the step 2) into hexadecyltrimethylamine bromide, water, a phenol compound, absolute ethyl alcohol, ammonia water and an aldehyde compound, and stirring for 5-10 hours at the temperature of 20-70 ℃; filtering and washing; wherein the phenol compound is one of phenol, m-triphenyl phenol, p-phenol and o-phenol; the aldehyde compound is one of acetaldehyde, propionaldehyde and butyraldehyde; the molar ratio of the iron element to the phenol compound is 0.5-5; the molar ratio of the phenol compound to the aldehyde compound is 1-1.5;
4) putting the product of the step 3) in N2Carbonizing at the temperature of 800 ℃ for 2-10h under the atmosphere of 400-;
5) repeating the product of the step 4) for 1-3 times of circulation of the step 1, the step 2, the step 3 and the step 4;
6) putting the product obtained in the step 5) into a strong alkali solution for 5-10 hours; washing and drying;
7) mixing the product obtained in the step 6) with iodine, and carrying out solid solution at the temperature of 100-200 ℃ for 2-10 hours; then solid solution is carried out for 1-5 hours at the temperature of 400-800 ℃; obtaining the iron-based-carbon lithium ion battery composite electrode material with a core-shell structure; the molar ratio of iodine to iron is 0.2-1.2.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009021102A (en) * | 2007-07-12 | 2009-01-29 | Toyota Central R&D Labs Inc | Lithium-ion secondary battery |
CN102646817A (en) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | Graphene/metal oxide composite cathode material for lithium ion battery and preparation |
KR20140130361A (en) * | 2013-04-05 | 2014-11-10 | 주식회사 인트론바이오테크놀로지 | Metal oxide nanoparticle-based magnetic resonance imaging contrast agent with a central cavity |
CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
CN106531990A (en) * | 2016-11-07 | 2017-03-22 | 北京圣盟科技有限公司 | Preparation method for graphene composite electrode material for lithium ion battery |
CN107275624A (en) * | 2017-07-24 | 2017-10-20 | 扬州大学 | The preparation method of carbon coating spindle shape iron oxide composite material of core-shell structure |
CN107507686A (en) * | 2017-08-31 | 2017-12-22 | 扬州大学 | A kind of preparation method of magnetic nano cages |
-
2020
- 2020-05-12 CN CN202010395414.4A patent/CN111540892B/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009021102A (en) * | 2007-07-12 | 2009-01-29 | Toyota Central R&D Labs Inc | Lithium-ion secondary battery |
CN102646817A (en) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | Graphene/metal oxide composite cathode material for lithium ion battery and preparation |
KR20140130361A (en) * | 2013-04-05 | 2014-11-10 | 주식회사 인트론바이오테크놀로지 | Metal oxide nanoparticle-based magnetic resonance imaging contrast agent with a central cavity |
CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
CN106531990A (en) * | 2016-11-07 | 2017-03-22 | 北京圣盟科技有限公司 | Preparation method for graphene composite electrode material for lithium ion battery |
CN107275624A (en) * | 2017-07-24 | 2017-10-20 | 扬州大学 | The preparation method of carbon coating spindle shape iron oxide composite material of core-shell structure |
CN107507686A (en) * | 2017-08-31 | 2017-12-22 | 扬州大学 | A kind of preparation method of magnetic nano cages |
Non-Patent Citations (2)
Title |
---|
A Cast-Mold Approach to Iron Oxide and Pt/Iron Oxide Nanocontainers and Nanoparticles with a Reactive Concave Surface;George, Chandramohan等;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》;20110126;第133卷(第7期);第2205-2217页 * |
金属碘化物低温还原石墨烯氧化物制备石墨烯薄膜;刘辰洋;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20151015;第2015卷(第10期);第B014-3页 * |
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