CN105776130A - Preparation method for hollow porous carbon composite material - Google Patents
Preparation method for hollow porous carbon composite material Download PDFInfo
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- CN105776130A CN105776130A CN201610120766.2A CN201610120766A CN105776130A CN 105776130 A CN105776130 A CN 105776130A CN 201610120766 A CN201610120766 A CN 201610120766A CN 105776130 A CN105776130 A CN 105776130A
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- carbon composite
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001338 self-assembly Methods 0.000 claims description 5
- 235000001014 amino acid Nutrition 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000003544 oxime group Chemical group 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 238000001149 thermolysis Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000004146 energy storage Methods 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000005540 biological transmission Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- JGUQDUKBUKFFRO-GGWOSOGESA-N (NE)-N-[(3E)-3-hydroxyiminobutan-2-ylidene]hydroxylamine Chemical compound O\N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-GGWOSOGESA-N 0.000 description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 238000002076 thermal analysis method Methods 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- -1 aromatic aldehyde oxime Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HRSADIZPZPRZEI-UHFFFAOYSA-L zinc;diacetate;hydrate Chemical compound O.[Zn+2].CC([O-])=O.CC([O-])=O HRSADIZPZPRZEI-UHFFFAOYSA-L 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 206010016807 Fluid retention Diseases 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for a hollow porous carbon composite material. The preparation method comprises the following steps that 1, solid phases are self-assembled to synthesize a metal complex; 2, the metal complex is subjected to in-situ thermolysis and carbothermic reduction to synthesize the hollow porous carbon composite material with embedded metal or metal oxide nano-particles. Furthermore, the carbon composite material is modified and reacts with proper acid, the metal or metal oxide nano-particles in the carbon composite material are removed, and then a graded porous carbon composite material is further obtained. According to the preparation method, a simple one-pot solid-phase reaction method is adopted, step-by-step temperature control is carried out, and then the hollow porous carbon composite material with the evenly embedded metal or metal oxide nano-particles is obtained. Various carbon composite materials synthesized through the method have the advantages of being good in charge and discharge capacity stability, high in specific capacity, excellent in rate capability and the like, and can be applied to lithium ion batteries, electrochemical capacitors and new energy fields.
Description
Technical field
The preparation method that the present invention relates to a kind of electrode material, preparation method particularly to a kind of hollow porous carbon composite, prepared composite is the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles, or the carbon composite to its modified part or all of removing metal or the graded porous structure of metal-oxide.
Background technology
Along with growth and the expanding economy of social population, global energy shortage is day by day serious, and environment worsens increasingly, and the development of new forms of energy is proposed an urgent demand by people.Energy storage technology as it have been recognized that one of the effective measures of development new forms of energy, receive the unprecedented attention of national governments, significantly promoted the development of energy storage technology industry and the exploitation application of scale energy storage technology.
Energy storage technology currently mainly has physics energy storage (such as water-retention energy storage, compressed-air energy storage, flywheel energy storage etc.), chemical energy storage (such as lead-acid battery, nickel-cadmium cell etc.) and other energy storage modes (such as Power Flow, phase-change accumulation energy etc.).From energy storage implementation, chemical energy storage sharpest edges compared with other types energy storage technology are in that the multiformity of implementation, thus result in that performance difference is huge, the marketization of the research and development of the numerous and complicated various chemical energy storage battery of type and product；From performance, comparing other energy storage types, chemical energy storage has the common features such as volume is little, response speed is fast, easy for installation.Just because of these advantages, chemical energy storage technology has been widely used for the facilities such as Large UPS, macro base stations and family's building, and is expected to be applied on a large scale in following intelligent grid, electric automobile.
The chemical energy storage technology having been carried out commercial applications has lead-acid battery, Ni-MH battery, sodium-sulphur battery, vanadium flow battery etc., also have some chemical energy storage technology researched and developed, wherein lithium ion battery, sodium-ion battery, electrochemical capacitor be it is believed that it is star of hope in new chemical energy storage technology, especially lithium ion battery, the new chemical energy that it rose as the nineties in 20th century, there is energy density height, self discharge is little, have extended cycle life, memory-less effect and the advantage such as environmental pollution is little, it is widely used in mobile phone, notebook computer, video camera, in the portable electronic products such as digital camera, in energy storage, communication, space flight, each field such as electric motor car also has broad application prospects.
But, in these new chemical energy storage technologies that people have explored, the electrode material used is mainly based on graphite, and its theoretical specific capacity is 372mAhg-1, limit the further raising of its capacity；Embedding simultaneously because its embedding lithium (sodium) mode is generally section, being not suitable for fast charging and discharging, thus limiting its application in high power field.Therefore, explore and offer has new carbon of advantage such as charge/discharge capacity good stability, specific capacity is high, high rate performance is superior and preparation method thereof, just can be expected to break through the bottleneck of new chemical energy storage technology.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of hollow porous carbon composite, described method can prepare the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles, being modified further, partly or entirely removing metal or metal-oxide thus obtaining the carbon composite of graded porous structure.The method adopts easy " one pot " solid reaction process, uniformly it is inlaid with the hollow porous carbon composite of metal or metal oxide nanoparticles by the synthesis of substep temperature control, removes metal therein or metal oxide nanoparticles can obtain classifying porous carbon modified composite further.The various carbon composites of described method synthesis can be used as electrode material, has the advantages such as charge/discharge capacity good stability, specific capacity is high, high rate performance is superior.
The purpose of the present invention is realized by following measures:
The preparation method of a kind of hollow porous carbon composite, comprises the following steps:
(1) solid phase self assembly metal complex: with solid metal salt for source metal, with solid organic matters part or its presoma for carbon source, slaine is ground with Organic substance part and mixs homogeneously, then by the temperature reaction under an inert atmosphere of described mixture, self assembly metal complex；
(2) metal complex in-situ heat is decomposed and carbon thermal reduction: under an inert atmosphere, metal complex step (1) prepared continues temperature reaction, metal complex generation in-situ heat is made to decompose and carbon reduction, reaction terminates rear natural cooling, prepares the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles.
Preferably,
In step (1), described slaine is identical with the mol ratio of part with metal ion in metal complex with the mol ratio of Organic substance part.
In step (1), described slaine is the acetate of Fe, Co, Ni, Cu, Zn, Sb or Pb, oxalates, sulfate, nitrate or chloride.If solid salt contains water of crystallization, it is not necessary to remove water of crystallization therein.
In step (1), described Organic substance part includes oxime, arylamine, Schiff's base, dimerization or the solids such as tripolycyanamide, aminoacid.Wherein oxime adopts common oxime, such as diacetyldioxime, aromatic aldehyde oxime, arone oxime；Arylamine can be phenylenediamine (including o-phenylenediamine, m-diaminobenzene., p-phenylenediamine and derivant thereof) or other arylamine solids；Schiff's base is the solid matter of various aldehydes or ketones and amine condensation gained；Aminoacid is common amino acid solid, such as glycine, alanine, phenylalanine, tryptophan, arginine or histidine etc..Organic substance part can also adopt its precursor, as Schiff's base be aldehydes or ketones compound with the direct solid state reaction original position condensation of amines and obtain, therefore, aldehydes or ketones compounds and aminated compounds are the precursors of Schiff's base.
In step (1), described reaction temperature is less than 100 DEG C；Response time is 1～10h.
In step (2), described reaction temperature is 300～1000 DEG C；Response time is 1～24h.
In described step (1) and step (2), inert atmosphere is N2Or noble gas, it is preferred to N2Or Ar.
The core of the inventive method is in that under substep temperature control " one pot " solid state reaction controls synthesis, under inert gas shielding, first under low heating temperature, and source metal and carbon source solid phase self assembly in-situ preparation metal complex；At high temperature make metal complex generation in-situ heat decompose and carbon thermal reduction subsequently, prepare the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles.
Further, the prepared hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles is modified, it is about to the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles under hydrothermal conditions by acid etch, partly or entirely remove the metal in described carbon composite or metal oxide nanoparticles, prepare the hollow porous carbon composite with graded porous structure.
Preferably, hydrothermal condition is, temperature is 60～180 DEG C, and the time is 1～24h.
The acid of described etching is hydrochloric acid, sulphuric acid, nitric acid or Fluohydric acid.；The concentration of described acid is 0.1～4molL-1。
In the inventive method, the reason that the described hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles generates is, when low heating temperature, slaine and organic ligand or its presoma generation complexation reaction, primary reconstruction generates metal complex；This metal complex is under the high temperature conditions, original position there occurs thermal decomposition, form carbon skeleton (network) structure of composite, being simultaneously generated the metal-oxide of nanoscale or the metal simple-substance of the nanoscale of metal ion in-situ reducing one-tenth generation, prepared nano metal or metal oxide particle are uniformly embedded in material with carbon element.Additionally, leave substantial amounts of hole after the gaseous volatilization of the thermal decomposition generation of metal complex, therefore, the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles just can obtain.
It is an advantage of the current invention that:
(1) present invention adopts substep one pot of solid reaction process of temperature control, first in-situ preparation metal complex, and under high temperature subsequently, there is thermal decomposition and carbon thermal reduction, prepare the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles；Described preparation method is easy, environmentally friendly, has universal, it is adaptable to each metal complexes is the synthesis of the carbon composite of precursor, it is possible to accomplish scale production.
(2) metal in the carbon composite synthesized by the present invention or metal oxide nanoparticles, it is possible to by partly or entirely being etched removal with suitable acid reaction, therefore can obtain classifying porous carbon modified composite further；And this method of modifying is simple, convenient, be suitable for large-scale production.
(3) the various carbon composites synthesized by the present invention have the advantages such as charge/discharge capacity good stability, specific capacity is high, high rate performance is superior as electrode material, can be used for the new energy fields such as lithium ion battery, sodium-ion battery, electrochemical capacitor.
Accompanying drawing explanation
Fig. 1 is the H-NiN-CNetworkX x ray diffraction collection of illustrative plates of embodiment 1 synthesis.
Fig. 2 is the H-NiN-CNetwork thermal analysis curve of embodiment 1 synthesis.
Fig. 3 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of the H-NiN-CNetwork of embodiment 1 synthesis.(Fig. 3-a is H-NiN-CNetwork scanning electron microscope (SEM) photograph, scale=2 μm；Fig. 3-b is H-NiN-CNetwork transmission electron microscope picture, scale=1 μm；Fig. 3-c is H-NiN-CNetwork transmission electron microscope picture, scale=200nm；Fig. 3-d is H-NiN-CNetwork transmission electron microscope picture, scale=5nm).
Fig. 4 is the distribution diagram of element of the dark field transmission Electronic Speculum figure of H-NiN-CNetwork of embodiment 1 synthesis and respective regions.(Fig. 4-a is the dark field transmission Electronic Speculum figure of H-NiN-CNetwork；Fig. 4-b is respective regions Ni distribution diagram of element；Fig. 4-c is respective regions C element scattergram；Fig. 4-d is respective regions N element scattergram).
Fig. 5 is the X ray diffracting spectrum of the L-NiN-CNetwork of the 2-in-1 one-tenth of embodiment.
Fig. 6 is the thermal analysis curve of the L-NiN-CNetwork of the 2-in-1 one-tenth of embodiment.
Fig. 7 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of the L-NiN-CNetwork of the 2-in-1 one-tenth of embodiment.(Fig. 7-a is L-NiN-CNetwork scanning electron microscope (SEM) photograph, scale=2 μm；Fig. 7-b is L-NiN-CNetwork transmission electron microscope picture, scale=1 μm；Fig. 7-c is L-NiN-CNetwork transmission electron microscope picture, scale=50nm；Fig. 7-d is L-NiN-CNetwork transmission electron microscope picture, scale=5nm).
Fig. 8 is the distribution diagram of element of the dark field transmission Electronic Speculum figure of the L-NiN-CNetwork of the 2-in-1 one-tenth of embodiment and respective regions.(Fig. 8-a is the dark field transmission Electronic Speculum figure of L-NiN-CNetwork；Fig. 8-b is respective regions Ni distribution diagram of element；Fig. 8-c is respective regions C element scattergram；Fig. 8-d is respective regions N element scattergram).
Fig. 9 be in the H-NiN-CNetwork of synthesis in embodiment 1 and embodiment 2 the L-NiN-CNetwork material of synthesis as the circulation volume figure of lithium ion battery negative material.
Figure 10 be in the H-NiN-CNetwork of synthesis in embodiment 1 and embodiment 2 the L-NiN-CNetwork material of synthesis as the high rate performance figure of lithium ion battery negative material.
Detailed description of the invention
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with detailed description of the invention, but is defined in the claims.
Embodiment 1
Weigh 7.5mmol nickel acetate tetrahydrate and 15mmol diacetyldioxime, grind respectively in agate mortar under room temperature after uniformly, then by uniform for both mixed grindings.This mixture is transferred to burning boat, then burning boat is pushed in tube furnace, at N2Under atmosphere, with 5 DEG C of min-1Heating rate be warmed up to 60 DEG C, and keep 5h at such a temperature.Thereafter again with 3 DEG C of min-1Heating rate be warmed up to 650 DEG C, and keep 4h at such a temperature.After cooling to room temperature with stove afterwards, just be uniformly inlaid with the hollow porous nitrogen-doped carbon composite of high-load Ni nano-particle, this sample is designated as H-NiN-CNetwork.
Fig. 1 is the H-NiN-CNetworkX x ray diffraction collection of illustrative plates of the present embodiment synthesis.Result shows, containing W metal (JCPDSNo.65-0380) in H-NiN-CNetwork material, Ni nano-particles size is approximately 20nm (utilizing Scherrer formula to calculate to obtain, this result is consistent with the result recorded in the transmission electron microscope picture of Fig. 3-c).
Fig. 2 is the H-NiN-CNetwork that the present embodiment the synthesizes thermal analysis curve recorded in air atmosphere.Result shows, in H-NiN-CNetwork, the content of carbon is about 8.8wt%, it is seen then that in H-NiN-CNetwork, the content of Ni is very high.
Fig. 3 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of the H-NiN-CNetwork of the present embodiment synthesis.Wherein Fig. 3-a is scanning electron microscope (SEM) photograph, and Fig. 3-b, 3-c, 3-d are the transmission electron microscope pictures under different amplification.Fig. 3-a, 3-b, 3-c show that H-NiN-CNetwork is the network structure material of a hollow porous, uniform embedding nickel, and Ni is evenly distributed in network structure.Fig. 3 d figure shows the lattice fringe of Ni (111) crystal face, and spacing is 0.21nm.
Fig. 4 is the distribution diagram of element of the dark field transmission Electronic Speculum figure of H-NiN-CNetwork of the present embodiment synthesis and respective regions.The figure illustrates the nitrogen-doped carbon composite that H-NiN-CNetwork is a hollow porous, uniform embedding nickel, tri-kinds of elements of C, N, Ni are uniformly distributed, and wherein Fig. 4-b, 4-c, 4-d respectively illustrate the distribution situation of tri-kinds of elements of Ni, C, N.
Visible, the material of above-mentioned synthesis is hollow porous, uniformly inlays high content nickel, has the nitrogen-doped carbon composite (H-NiN-CNetwork) of network structure, its Producing reason is, at 60 DEG C, nickel acetate tetrahydrate and diacetyldioxime generation complexation reaction, primary reconstruction generates solid complexes nickel dimethylglyoximate；This coordination compound is at 650 DEG C, and original position there occurs thermal decomposition, and metallic nickel ions in-situ reducing has also been become the simple substance Ni of nanoscale by the carbon of generation, and Ni nanoparticle granule is uniformly embedded in the material with carbon element of N doping.Additionally, leave substantial amounts of hole after the gaseous volatilization that the thermal decomposition of solid complexes produces, therefore, hollow porous, the nitrogen-doped carbon composite uniformly inlaying nickel just can obtain.
Embodiment 2
By the H-NiN-CNetwork ultrasonic disperse that obtains in 0.3g embodiment 1 at 20mL, 1molL-1Hydrochloric acid solution in, be then transferred in 40mL reactor, at 80 DEG C, keep 10h.After naturally cooling to room temperature, obtaining the hollow porous nitrogen-doped carbon composite being uniformly inlaid with low content Ni nano-particle, this sample is designated as L-NiN-CNetwork.
Fig. 5 is the X ray diffracting spectrum of the L-NiN-CNetwork of the present embodiment synthesis.Result shows, still contains W metal in L-NiN-CNetwork material, but wherein little than before acid etch of the particle size of Ni, for 8nm (utilizing Scherrer formula to calculate to obtain, this result is consistent with the result recorded in Fig. 7-d transmission electron microscope picture).
Fig. 6 is the L-NiN-CNetwork that the present embodiment the synthesizes thermal analysis curve recorded in air atmosphere.Result shows, in L-NiN-CNetwork, the content of carbon is about 69.6wt%, it is seen then that through the etching processing of peracid, and in H-NiN-CNetwork, Ni major part is eliminated by reaction, and therefore in the sample after etching processing, the content of carbon can be greatly promoted.
Fig. 7 is scanning electron microscope (SEM) photograph and the transmission electron microscope picture of the L-NiN-CNetwork of the present embodiment synthesis.Fig. 7-a is scanning electron microscope (SEM) photograph, and Fig. 7-b, 7-c, 7-d are the transmission electron microscope picture under different amplification.Fig. 7-a, 7-b, 7-c show that L-NiN-CNetwork is the network structure material of a hollow porous.Fig. 7-d figure shows the lattice fringe of Ni (111) crystal face, and spacing is 0.21nm.
Fig. 8 is the distribution diagram of element of the dark field transmission Electronic Speculum figure of L-NiN-CNetwork of the present embodiment synthesis and respective regions.The figure illustrates the nitrogen-doped carbon composite that L-NiN-CNetwork is the embedding nickel of hollow porous, tri-kinds of elements of C, N, Ni are uniformly distributed, and Fig. 8-b, 8-c, 8-d respectively illustrate tri-kinds of elemental distribution of Ni, C, N.
Fig. 9 be in the H-NiN-CNetwork of synthesis in embodiment 1 and the present embodiment the L-NiN-CNetwork material of synthesis as the circulation volume figure of lithium ion battery negative material.As seen from the figure, the specific capacity of L-NiN-CNetwork negative material is far above H-NiN-CNetwork；After discharge and recharge 100 is enclosed, L-NiN-CNetwork still keeps 885.2mAhg-1Specific capacity.
Figure 10 be in the H-NiN-CNetwork of synthesis in embodiment 1 and the present embodiment the L-NiN-CNetwork material of synthesis as the high rate performance figure of lithium ion battery negative material.As seen from the figure, the high rate performance of L-NiN-CNetwork and H-NiN-CNetwork negative material is all very superior, imply that and adopts both materials to go for high power field as the lithium ion battery of negative pole.
Embodiment 3
Weigh 12.5mmol bis-acetate hydrate zinc and 25mmol diacetyldioxime, grind respectively in agate mortar under room temperature after uniformly, then both are mixed, grinds uniformly.This mixture is transferred to burning boat, then burning boat is pushed in tube furnace, under an ar atmosphere, with 5 DEG C of min-1Heating rate be warmed up to 50 DEG C, and keep 7h at such a temperature.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 500 DEG C, and keep 7h at such a temperature.After cooling to room temperature with stove afterwards, obtain the hollow porous carbon composite being uniformly inlaid with ZnO nano granule.
The prepared hollow porous carbon composite being uniformly inlaid with ZnO nano granule is similar to embodiment 1,2, and to carry out acid etch modified and characterize, conclusion and embodiment 1,2 basic simlarity.
Embodiment 4
Weigh 2mmol Iron(III) chloride hexahydrate, 2mmol o-phenylenediamine and 4mmol o-vanillin, grind respectively in agate mortar under room temperature after uniformly, then three is mixed, grinds uniformly.This mixture is transferred to burning boat, then burning boat is pushed in tube furnace, at N2Under atmosphere, with 5 DEG C of min-1Heating rate temperature programming to 40 DEG C, and keep 8h at such a temperature.Thereafter again with 10 DEG C of min-1Heating rate be warmed up to 550 DEG C, and keep 6h at such a temperature.After cooling to room temperature with stove afterwards, obtain the hollow porous carbon composite being uniformly inlaid with Fe nano-particle.
The prepared hollow porous carbon composite being uniformly inlaid with Fe nano-particle is similar to embodiment 1,2, and to carry out acid etch modified and characterize, conclusion and embodiment 1,2 basic simlarity.
Embodiment 5
Weigh 2mmol tetra-acetate hydrate cobalt, 2mmol o-phenylenediamine and 4mmol o-vanillin, grind respectively in agate mortar under room temperature after uniformly, then three is mixed, grinds uniformly.This mixture is transferred to burning boat, then burning boat is pushed in tube furnace, under an ar atmosphere, with 5 DEG C of min-1Heating rate be warmed up to 55 DEG C, and keep 6h at such a temperature.Thereafter again with 10 DEG C of min-1Heating rate be warmed up to 700 DEG C, and keep 5h at such a temperature.After cooling to room temperature with stove afterwards, obtain the hollow porous carbon composite being uniformly inlaid with Co nano-particle.
The prepared hollow porous carbon composite being uniformly inlaid with Co nano-particle is similar to embodiment 1,2, and to carry out acid etch modified and characterize, conclusion and embodiment 1,2 basic simlarity.
Embodiment 6
Weigh 2mmol bis-acetate hydrate zinc and 4mmol glycine, grind respectively in agate mortar under room temperature after uniformly, then both are mixed, grinds uniformly.This mixture is transferred to burning boat, then burning boat is pushed in tube furnace, under an ar atmosphere, with 5 DEG C of min-1Heating rate be warmed up to 60 DEG C, and keep 5h at such a temperature.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 600 DEG C, and keep 3h at such a temperature.After cooling to room temperature with stove afterwards, obtain the hollow porous carbon composite being uniformly inlaid with ZnO nano granule.
The prepared hollow porous carbon composite being uniformly inlaid with ZnO nano granule is similar to embodiment 1,2, and to carry out acid etch modified and characterize, conclusion and embodiment 1,2 basic simlarity.
Embodiment 7
Weigh 3mmol nickel acetate tetrahydrate and 2mmol tripolycyanamide, grind respectively in agate mortar under room temperature after uniformly, then both are mixed, grinds uniformly.This mixture is transferred to burning boat, then burning boat is pushed in tube furnace, under an ar atmosphere, with 5 DEG C of min-1Heating rate be warmed up to 50 DEG C, and keep 5h at such a temperature.Thereafter again with 5 DEG C of min-1Heating rate be warmed up to 500 DEG C, and keep 3h at such a temperature.After cooling to room temperature with stove afterwards, obtain the hollow porous carbon composite being uniformly inlaid with Ni nano-particle.
The prepared hollow porous carbon composite being uniformly inlaid with Ni nano-particle is similar to embodiment 1,2, and to carry out acid etch modified and characterize, conclusion and embodiment 1,2 basic simlarity.
Claims (9)
1. the preparation method of a hollow porous carbon composite, it is characterised in that said method comprising the steps of:
(1) solid phase self assembly metal complex: with solid metal salt for source metal, with solid organic matters part or its presoma for carbon source, slaine is ground with Organic substance part and mixs homogeneously, then by the temperature reaction under an inert atmosphere of described mixture, self assembly metal complex；
(2) metal complex in-situ heat is decomposed and carbon thermal reduction: under an inert atmosphere, metal complex step (1) prepared continues temperature reaction, metal complex generation in-situ heat is made to decompose and carbon reduction, reaction terminates rear natural cooling, prepares the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles.
2. the preparation method of hollow porous carbon composite according to claim 1, it is characterised in that described method also includes:
(3) acid etch modifiies: the hollow porous carbon composite being uniformly inlaid with metal or metal oxide nanoparticles step (2) prepared is under hydrothermal conditions by acid etch, partly or entirely remove the metal in described carbon composite or metal oxide nanoparticles, prepare the hollow porous carbon composite with graded porous structure.
3. the preparation method of hollow porous carbon composite according to claim 1 and 2, it is characterised in that in step (1), described slaine is identical with the mol ratio of part with metal ion in metal complex with the mol ratio of Organic substance part.
4. the preparation method of hollow porous carbon composite according to claim 1 and 2, it is characterized in that, in step (1), described slaine is the acetate of Fe, Co, Ni, Cu, Zn, Sb or Pb, oxalates, sulfate, nitrate or chloride；Described Organic substance part is selected from oxime, arylamine, Schiff's base, dimerization or tripolycyanamide or aminoacid.
5. the preparation method of hollow porous carbon composite according to claim 1 and 2, it is characterised in that in step (1), described reaction temperature is less than 100 DEG C；Response time is 1～10h.
6. the preparation method of hollow porous carbon composite according to claim 1 and 2, it is characterised in that in step (2), described reaction temperature is 300～1000 DEG C；Response time is 1～24h.
7. the preparation method of hollow porous carbon composite according to claim 1 and 2, it is characterised in that described step (1) and in step (2) inert atmosphere be N2Or noble gas.
8. the preparation method of hollow porous carbon composite according to claim 2, it is characterised in that hydrothermal condition is temperature 60～180 DEG C, and the time is 1～24h.
9. the preparation method of hollow porous carbon composite according to claim 2, it is characterised in that the acid of described etching is hydrochloric acid, sulphuric acid, nitric acid or Fluohydric acid.；The concentration of described acid is 0.1～4molL-1。
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