CN108574093B - Carbon/titanium pyrophosphate composite material and preparation method thereof - Google Patents
Carbon/titanium pyrophosphate composite material and preparation method thereof Download PDFInfo
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- BDVMTRCCIQHRBL-UHFFFAOYSA-J phosphonato phosphate;titanium(4+) Chemical compound [Ti+4].[O-]P([O-])(=O)OP([O-])([O-])=O BDVMTRCCIQHRBL-UHFFFAOYSA-J 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 13
- 239000000084 colloidal system Substances 0.000 description 13
- 238000000635 electron micrograph Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910000857 LiTi2(PO4)3 Inorganic materials 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910001194 LixV2O5 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910001310 TiP2O7 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 VO2 Chemical compound 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 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
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- 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)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of a carbon/titanium pyrophosphate composite material, which comprises the following steps: the method comprises the following steps: preparing polystyrene-acrylic acid colloidal aqueous dispersion for later use; step two: adding cetyl trimethyl ammonium bromide and polystyrene-acrylic acid colloidal aqueous dispersion into ethanol under stirring at room temperature to form uniform dispersion; then, sequentially dripping tetrabutyl titanate and phosphoric acid into the solution, and continuously stirring for 10-30 min; step three: magnetically stirring and heating the mixture obtained in the step two in a 70-90 ℃ silicon oil bath, and carrying out sol-gel reaction until ethanol is completely evaporated to obtain a white solid; step four: and (3) heating the solid obtained in the step three from room temperature to 700-800 ℃ at the speed of 1-5 ℃/min under the protection of high-purity argon, carrying out high-temperature heat treatment at the temperature of 700-800 ℃ for 4-6 h, and then cooling to room temperature to obtain a black product, namely the finished product of the carbon/titanium pyrophosphate composite material. The carbon/titanium pyrophosphate composite material prepared by the method has excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials of water-based lithium ion batteries, in particular to a carbon/titanium pyrophosphate composite material and a preparation method thereof.
Background
Lithium ion batteries have the advantages of high energy density and high operating voltage, and have been widely used in various electronic devices and instruments (chem. soc. rev., 2015, 44, 5926-. However, the traditional organic lithium ion battery has the defects of low safety coefficient, heavy environmental pollution, higher cost and the like. In recent years, the developed aqueous lithium ion battery overcomes the defects of the traditional organic lithium ion battery by using an aqueous electrolyte instead of an organic electrolyte, and becomes a novel chemical power source with great development potential (adv. Energy mater, 2012, 2, 830-840.). And itSimilar to his chemical power source, the battery capacity and overall performance of aqueous lithium ion batteries are also limited by the type, structure and properties of the electrode materials. At present, spinel LiMn2O4Layered LiCoO2Layered LiNiO2、LiNi1/3Mn1/3Co1/3O2Olivine LiFePO4、MnO2Is the most typical cathode material. Oxides of vanadium such as VO2、LiV3O8、LixV2O5、V2O5And polyphosphates of titanium of the NASICON type and lithium salts thereof such as TiP2O7、LiTi2(PO4)3Is the most typical anode material (adv. Energy mater, 2012, 2, 830-.
Among them, titanium pyrophosphate (TiP)2O7) Since first proposed in 2007, it has been considered as a very promising anode material for aqueous lithium ion batteries, and has attracted a great interest in the industry and academia. The material, as a polyanion compound, has a cubic structure similar to that of the NaCl type, in which TiO is present6Octahedron and P2O7The double tetrahedrons are connected through a vertex angle. This open polyanion network facilitates rapid lithium ion transport, thereby providing titanium pyrophosphate with good electrochemical activity and thermal stability. However, titanium pyrophosphate generally has relatively low electronic conductivity, resulting in poor cycle stability and rate capability (ACS appl. mater. Interfaces 2017, 9, 8075-8082).
The combination of titanium pyrophosphate and carbon to form carbon/titanium pyrophosphate composite material, which improves the conductivity, has become a feasible method for improving the electrochemical performance of titanium pyrophosphate (Solid State Ionics 2013, 249-250, 72-77.; J.Mater. chem. A2016, 4 (35), 13390-13394.; J.electrochem. Soc. 2015, 162 (9), A1921-A1926.; Electrochem. Acta 2012, 75, 247-253.). The carbon source for preparing the carbon/titanium pyrophosphate composite material mainly comprises sucrose, graphite, graphene and other single substances, and has single functions and limited performance improvement range.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide a carbon/titanium pyrophosphate composite material with excellent electrochemical performance and a preparation method thereof.
A preparation method of a carbon/titanium pyrophosphate composite material comprises the following steps:
the method comprises the following steps: preparing polystyrene-acrylic acid colloidal aqueous dispersion for later use;
step two: adding cetyl trimethyl ammonium bromide and polystyrene-acrylic acid colloidal aqueous dispersion into ethanol under stirring at room temperature to form uniform dispersion; then, sequentially dripping tetrabutyl titanate and phosphoric acid into the solution, and continuously stirring for 10-30 min;
step three: magnetically stirring and heating the mixture obtained in the step two in a 70-90 ℃ silicon oil bath, and carrying out sol-gel reaction until ethanol is completely evaporated to obtain a white solid;
step four: and (3) heating the solid obtained in the step three from room temperature to 700-800 ℃ at the speed of 1-5 ℃/min under the protection of high-purity argon, carrying out high-temperature heat treatment at the temperature of 700-800 ℃ for 4-6 h, and then cooling to room temperature to obtain a black product, namely the finished product of the carbon/titanium pyrophosphate composite material.
Further, according to the preparation method of the carbon/titanium pyrophosphate composite material, the purity of the cetyl trimethyl ammonium bromide is 99%, the purity of the tetrabutyl titanate is more than 99%, the concentration of the phosphoric acid is 85wt%, and the concentration of the ethanol is 95%.
Further, according to the preparation method of the carbon/titanium pyrophosphate composite material, the room temperature in the second step is 20-30 ℃, the hexadecyl trimethyl ammonium bromide and the polystyrene-acrylic acid colloidal aqueous dispersion liquid in the second step are added at one time, the dropping speed of tetrabutyl titanate in the second step is 3-5 mL/min, the dropping speed of phosphoric acid in the second step is 3-5 mL/min, and the stirring in the second step and the third step is magnetic stirring at the speed of 100-300 r/min.
Further, in the above preparation method of the carbon/titanium pyrophosphate composite material, in the second step, the mass ratio of the hexadecyl trimethyl ammonium bromide to the polystyrene-acrylic acid colloidal aqueous dispersion, the tetrabutyl titanate, the phosphoric acid and the ethanol is 1: 25-45: 50-65: 35-45: 2000 to 3500.
Further, in the preparation method of the carbon/titanium pyrophosphate composite material, the high-temperature heat treatment in the fourth step is performed in a temperature-programmed tube furnace, and high-purity argon is introduced for 1 hour before the temperature programming is started to exhaust the air in the tube furnace.
Has the advantages that:
the method can prepare the carbon/titanium pyrophosphate composite material by three steps of stirring and mixing, sol-gel and high-temperature calcination, and has the characteristics of simple preparation process and equipment and excellent finished product performance;
in addition, the cetyl trimethyl ammonium bromide is a surfactant, can assist the growth of a micro-nano structure in the growth process of an inorganic material and can be used as a pore-forming template to form a pore structure, the surface of the poly (styrene-acrylic acid) colloid has negative charges, and the excessive aggregation of the titanium phosphate colloid can be inhibited to form a block through the interaction with the precursor titanium phosphate colloid.
In addition, the poly (styrene-acrylic acid) colloid is used as a carbon source, the decomposition temperature of the poly (styrene-acrylic acid) colloid is greatly higher than that of a small molecular carbon source, the carbon conversion rate and the retention rate are high, the composite material can obtain high enough carbon content, and the electrochemical performance of the composite material is improved.
Drawings
FIG. 1(a) is an electron micrograph of titanium pyrophosphate prepared without the addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid;
FIG. 1(b) is an electron micrograph of titanium pyrophosphate prepared without the addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid;
FIG. 2(a) is an electron micrograph of titanium pyrophosphate prepared with cetyltrimethylammonium bromide;
FIG. 2(b) is an electron micrograph of titanium pyrophosphate prepared with cetyltrimethylammonium bromide;
FIG. 3(a) is an electron micrograph of titanium pyrophosphate prepared with the simultaneous addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid;
FIG. 3(b) is an electron micrograph of titanium pyrophosphate prepared with the simultaneous addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of carbon/titanium pyrophosphate composite
Polystyrene-acrylic acid colloidal aqueous dispersion with mass concentration of 10.4% was prepared according to the document adv. Funct. Mater. 2012, 22, 1229-1235 for later use. At room temperature, 0.0285g of cetyltrimethylammonium bromide and 1.0g of polystyrene-acrylic acid colloidal aqueous dispersion were directly added to 80g of ethanol under magnetic stirring at 180 r/min to form a uniform dispersion. Subsequently, 1.70g of tetrabutyltitanate was added dropwise thereto at a rate of 4mL/min, and then 1.15g of phosphoric acid was added dropwise thereto at a rate of 4mL/min, with stirring continued for 20 min. And magnetically stirring and heating the obtained mixture at the temperature of 80 ℃ in a silicon oil bath for 180 r/min, and carrying out sol-gel reaction until ethanol is completely evaporated to obtain a white solid. And (3) heating the obtained solid from room temperature to 750 ℃ at the speed of 5 ℃/min under the protection of high-purity argon, carrying out high-temperature heat treatment at 750 ℃ for 5 hours, and then cooling to room temperature to obtain a black product, namely 0.95g of the finished carbon/titanium pyrophosphate composite material.
(2) Electrochemical performance test of carbon/titanium pyrophosphate composite material
Mixing the prepared composite material 0.0160g, acetylene black 0.0030g and polytetrafluoroethylene0.0010g of alkene (mass ratio 80: 15: 5), adding a small amount of water (0.1 mL), finely grinding to obtain uniform slurry, and pressing the slurry onto a stainless steel current collector by a tablet press to prepare the electrode. Before electrochemical property test, the electrode needs to be in 1M Li2SO4The solution was degassed under vacuum for 5 hours. Commercial activated carbon electrodes and saturated calomel electrodes were used as counter and reference electrodes, respectively. 1M Li at room temperature by three-electrode system2SO4In the electrolyte, a constant-current charge and discharge test (charge and discharge voltage range-0.8-0V) is carried out on the prepared electrode by using an electrochemical workstation (CHI 660E, Shanghai Chenghua device company).
According to the formulaC=I×△t/mAnd the corresponding specific capacity of the prepared sample under different discharge current densities can be calculated based on the discharge curveC. Wherein△t(h) The time of the discharge is shown as,I(mA) represents a discharge current of the discharge,m(g) representing the mass of active material in the electrode.
The result shows that under the current density of 100 mA/g, the specific discharge capacity of the prepared carbon/titanium pyrophosphate composite material can reach 68.7 mAh/g, which is higher than the specific discharge capacity of 48.1 mAh/g of the carbon/titanium pyrophosphate composite material prepared by taking hexadecyl trimethyl ammonium bromide as a single carbon source, and is much higher than the specific discharge capacity of 5.8 mAh/g of pure titanium pyrophosphate prepared without adding a carbon source. The carbon/titanium pyrophosphate composite material prepared by the method has excellent electrochemical performance and is a potential candidate for a cathode material of a water-based lithium ion battery.
Example 2
(1) Preparation of carbon/titanium pyrophosphate composite
Polystyrene-acrylic acid colloidal aqueous dispersion with mass concentration of 10.4% was prepared according to the document adv. Funct. Mater. 2012, 22, 1229-1235 for later use. At room temperature, 0.0285g of cetyltrimethylammonium bromide and 1.2g of polystyrene-acrylic acid colloidal aqueous dispersion were directly added to 90g of ethanol under magnetic stirring at 250 r/min to form a uniform dispersion. Subsequently, 1.80g of tetrabutyltitanate was added dropwise thereto at a rate of 5mL/min, and then 1.22g of phosphoric acid was added dropwise thereto at a rate of 5mL/min, with stirring continued for 10 min. And magnetically stirring and heating the obtained mixture at the temperature of 90 ℃ under a silicon oil bath for 250 r/min, and carrying out sol-gel reaction until the ethanol is completely evaporated to obtain a white solid. And (3) heating the obtained solid from room temperature to 700 ℃ at the speed of 3 ℃/min under the protection of high-purity argon, carrying out high-temperature heat treatment at 700 ℃ for 6 hours, and then cooling to room temperature to obtain a black product, namely 0.98g of the finished carbon/titanium pyrophosphate composite material.
(2) The procedure for testing the electrochemical properties of the resulting wood charcoal/titanium pyrophosphate composite material was the same as in example 1. The result shows that the specific discharge capacity of the prepared carbon/titanium pyrophosphate composite material can reach 65.2 mAh/g under the current density of 100 mA/g, is higher than the specific discharge capacity of the carbon/titanium pyrophosphate composite material prepared by taking hexadecyl trimethyl ammonium bromide as a single carbon source by 44.5mAh/g, and is much higher than the specific discharge capacity of pure titanium pyrophosphate prepared without adding a carbon source by 5.6 mAh/g, and the carbon/titanium pyrophosphate composite material prepared by the method has excellent electrochemical performance.
Example 3
(1) Preparation of carbon/titanium pyrophosphate composite
A10.4% by weight aqueous poly (styrene-acrylic acid) colloidal dispersion was prepared in accordance with Adv. Funct. Mater. 2012, 22, 1229-1235 and was ready for use. Cetyl trimethylammonium bromide (0.03 g) and poly (styrene-acrylic acid) colloidal aqueous dispersion (0.9 g) were added directly to 70g of ethanol at room temperature under magnetic stirring at 150 r/min to form a homogeneous dispersion. Subsequently, 1.60g of tetrabutyltitanate was added dropwise thereto at a rate of 3mL/min, and then 1.08g of phosphoric acid was added dropwise thereto at a rate of 3mL/min, with stirring continued for 30 min. And magnetically stirring and heating the obtained mixture at the temperature of 70 ℃ under a silicon oil bath for 150 r/min, and carrying out sol-gel reaction until the ethanol is completely evaporated to obtain a white solid. And (3) heating the obtained solid from room temperature to 800 ℃ at the speed of 4 ℃/min under the protection of high-purity argon, carrying out high-temperature heat treatment at 800 ℃ for 4 hours, and then cooling to room temperature to obtain a black product, namely 0.90g of the finished carbon/titanium pyrophosphate composite material.
(2) The procedure for testing the electrochemical properties of the resulting wood charcoal/titanium pyrophosphate composite material was the same as in example 1. The result shows that the specific discharge capacity of the prepared carbon/titanium pyrophosphate composite material can reach 63.1 mAh/g under the current density of 100 mA/g, is higher than the specific discharge capacity of the carbon/titanium pyrophosphate composite material prepared by taking hexadecyl trimethyl ammonium bromide as a single carbon source by 43.0mAh/g, and is much higher than the specific discharge capacity of pure titanium pyrophosphate prepared without adding a carbon source by 5.3 mAh/g, and the carbon/titanium pyrophosphate composite material prepared by the method has excellent electrochemical performance.
FIG. 1(b) is an electron micrograph of titanium pyrophosphate prepared without the addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid; FIG. 2(a) is an electron micrograph of titanium pyrophosphate prepared with cetyltrimethylammonium bromide; FIG. 2(b) is an electron micrograph of titanium pyrophosphate prepared with cetyltrimethylammonium bromide; FIG. 3(a) is an electron micrograph of titanium pyrophosphate prepared with the simultaneous addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid; FIG. 3(b) is an electron micrograph of titanium pyrophosphate prepared with the simultaneous addition of cetyltrimethylammonium bromide and poly (styrene-acrylic acid) colloid. As can be seen from the figures, the invention takes the cetyl trimethyl ammonium bromide and the poly (styrene-acrylic acid) colloid as raw materials, not only can provide a carbon source, but also can be used as a growth auxiliary agent to improve the microstructure of the titanium pyrophosphate, thereby greatly improving the electrochemical performance of the titanium pyrophosphate.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. A preparation method of a carbon/titanium pyrophosphate composite material is characterized by comprising the following steps:
the method comprises the following steps: preparing polystyrene-acrylic acid colloidal aqueous dispersion for later use;
step two: adding cetyl trimethyl ammonium bromide and polystyrene-acrylic acid colloidal aqueous dispersion into ethanol under stirring at room temperature to form uniform dispersion; then, sequentially dripping tetrabutyl titanate and phosphoric acid into the solution, and continuously stirring for 10-30 min;
step three: magnetically stirring and heating the mixture obtained in the step two in a 70-90 ℃ silicon oil bath, and carrying out sol-gel reaction until ethanol is completely evaporated to obtain a white solid;
step four: heating the solid obtained in the step three from room temperature to 700-800 ℃ at a speed of 1-5 ℃/min under the protection of high-purity argon, carrying out high-temperature heat treatment at 700-800 ℃ for 4-6 h, and then cooling to room temperature to obtain a black product, namely a finished product of the carbon/titanium pyrophosphate composite material;
and the room temperature in the second step is 20-30 ℃, the hexadecyl trimethyl ammonium bromide and the polystyrene-acrylic acid colloidal aqueous dispersion liquid in the second step are added at one time, the dropping speed of tetrabutyl titanate in the second step is 3-5 mL/min, the dropping speed of phosphoric acid in the second step is 3-5 mL/min, and the stirring in the second step and the third step is magnetic stirring at the speed of 100-300 r/min.
2. The method of preparing a carbon/titanium pyrophosphate composite material according to claim 1 wherein: the purity of the hexadecyl trimethyl ammonium bromide is 99%, the purity of the tetrabutyl titanate is more than 99%, the concentration of the phosphoric acid is 85wt%, and the concentration of the ethanol is 95%.
3. The method of preparing a carbon/titanium pyrophosphate composite material according to claim 1 wherein: in the second step, the mass ratio of the hexadecyl trimethyl ammonium bromide to the polystyrene-acrylic acid colloidal aqueous dispersion, the tetrabutyl titanate, the phosphoric acid and the ethanol is 1: 25-45: 50-65: 35-45: 2000-3500;
wherein the mass concentration of the polystyrene-acrylic acid colloidal aqueous dispersion is 10.4%.
4. The method of preparing a carbon/titanium pyrophosphate composite material according to claim 1 wherein: and the high-temperature heat treatment in the fourth step is carried out in a programmed temperature control tube furnace, and high-purity argon is introduced for 1 hour before the programmed temperature rise is started so as to discharge the air in the tube furnace.
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