CN112736236A - Novel biomass carbon-coated biphase Li serving as lithium ion battery negative electrode material4Ti5O12-TiO2And uses thereof - Google Patents
Novel biomass carbon-coated biphase Li serving as lithium ion battery negative electrode material4Ti5O12-TiO2And uses thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000002028 Biomass Substances 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910011956 Li4Ti5 Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010406 cathode material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 235000013399 edible fruits Nutrition 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 239000007773 negative electrode material Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 7
- 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 description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 230000002051 biphasic effect Effects 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 5
- 241001529253 Pterocarpus acapulcensis Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 241000565359 Fraxinus chinensis Species 0.000 abstract description 16
- 239000002114 nanocomposite Substances 0.000 abstract description 14
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910009866 Ti5O12 Inorganic materials 0.000 abstract description 3
- 239000002041 carbon nanotube Substances 0.000 abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 26
- 239000002244 precipitate Substances 0.000 description 10
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 241000223600 Alternaria Species 0.000 description 6
- 241000588214 Fraxinus chinensis subsp. rhynchophylla Species 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 241001446503 Pterocarpus Species 0.000 description 5
- 235000009984 Pterocarpus indicus Nutrition 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910010446 TiO2-a Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- 241001536358 Fraxinus Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 241000208140 Acer Species 0.000 description 1
- 235000001759 Citrus maxima Nutrition 0.000 description 1
- 244000276331 Citrus maxima Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000011201 Ginkgo Nutrition 0.000 description 1
- 235000008100 Ginkgo biloba Nutrition 0.000 description 1
- 244000194101 Ginkgo biloba Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910011965 Li4Ti5O12In Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 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
- H01M4/366—Composites as layered products
-
- 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
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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
- 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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/58—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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Abstract
The invention discloses a novel biomass carbon-coated biphase Li serving as a lithium ion battery cathode material4Ti5O12‑TiO2And applications thereof. The invention relates to a method for preparing Chinese ash tree wing peel by mixing Chinese ash tree wing peel with binary Li4Ti5O12‑TiO2The micro-nano composite material formed by the compound is applied to the lithium ion battery cathode material, and on one hand, the two-phase Li4Ti5O12‑TiO2The nano composite structure increases the grain boundary density of a large interface area, and on the other hand, the micron-sized carbonized fin peel has a macroporous structure, so that a network-shaped support is formed for a product, a conductive network can be provided, and Li can be reduced4Ti5O12、TiO2The agglomeration of the carbon nanotubes increases the active sites of the reaction, improves the electronegativity of the material, and thus improves the electrochemical performance of the material. The micro-nano composite material not only has a special structure, but also has the characteristics of a micron material and the special performance of a nano material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to biomass carbon-coated dual-phase Li4Ti5O12-TiO2The preparation method and the application of the novel lithium ion battery cathode material are provided.
Background
Rechargeable lithium ion batteries have high energy density and long cycle life and thus have been successfully used as power sources for portable electronic devices, while practical application storage of lithium ion batteries in electric vehicles and stationary electrical energy depends largely on the electrochemical properties of the electrode material, such as large specific capacity, high rate capacity and good cycle stability. Graphite is commonly used as the negative electrode of commercial lithium ion batteries, but because of its low Li+Diffusion coefficient and serious safety issues show poor rate performance. Li4Ti5O12(LTO) is one of the materials replacing graphite as the negative electrode, Li4Ti5O12Has a high theoretical specific capacity of 175mAh/g, and Li4Ti5O12In Li+No significant volume change occurs during the ion intercalation/deintercalation process. In addition to LTO, TiO2Is also one of the negative electrode replacement materials of lithium ion batteries because of its ability to insert/extract lithium faster during charge/discharge, high insertion potential (2.0V) and low volume change (3-4%), and TiO2The theoretical capacity of the catalyst is up to 336 mAh/g. However, LTO and TiO2All have some disadvantages, e.g. LTO shows low electronic, ionic conductivity and low rate capability, TiO2The diffusion rate is very low, which in turn affects the cycling and rate performance. Mixing LTO with TiO2Compounding has become an important and effective method to improve the performance of LTO electrodes. LTO-TiO synthesized by Raman (Rahman) et al molten salt method2Composite material with high capacity and good rate capability. Rutile-capped biphasic LTO-TiO synthesized by Wang et al2The composite material has higher capacity than pure LTO at various rates.
More recently, researchers have reported and demonstrated that biomass carbon can also be used in lithium ion batteries. The biomass carbon material has attracted extensive attention of researchers due to the advantages of porous structure, large specific surface area, good conductivity, rich sources, environmental friendliness and the like, and the biomass carbon material can be used as a high-conductivity material to be added into an electrode material to improve the electrochemical performance of the electrode material. Sun uses shaddock peel as the biomass carbon of the lithium ion battery negative electrode material, and the negative electrode material shows higher specific capacity. In addition, many different types of leaves are also used as biomass carbon for electrode materials, such as maple leaves, ginkgo leaves, and the like. In summary, biomass carbon has become very popular for use as an electrode material. The biomass carbon is added into the electrode material to provide a three-dimensional network structure, which can be Li+Provide convenient and efficient channels, increase the specific surface area of the electrode material, increase the contact area with the electrolyte, and result in high lithium ion flux across the electrolyte/electrode interface. In conclusion, the work provides a simple, economical and efficient method for battery materials and provides an important application prospect for the lithium ion battery cathode.
Disclosure of Invention
The invention aims to provide a novel biomass carbon-coated dual-phase Li serving as a lithium ion battery negative electrode material with good electrochemical performance4Ti5O12-TiO2The preparation method and the application thereof.
The invention provides a technical scheme that a novel biomass carbon-coated biphase Li serving as a lithium ion battery cathode material4Ti5O12-TiO2The preparation method comprises the following steps: mixing carbonized wing peel with LiOH. H2Ultrasonically dispersing O in deionized water, marking as a solution A, dispersing tetrabutyl titanate in an absolute ethyl alcohol solution, marking as a solution B, adding the solution A into the solution B, fully stirring and mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 12-36 h; collecting the precursor after hydrothermal treatmentThe bulk powder is cross-washed to neutrality by distilled water and ethanol, dried in vacuum for 24-36h at 80 ℃, then placed in a tube furnace, calcined for 1-3h at 800 ℃ under argon atmosphere and 600 ℃ and ground to obtain the target product biomass carbon-coated biphase Li4Ti5O12-TiO2A composite material.
Furthermore, the novel biomass carbon-coated dual-phase Li as the lithium ion battery cathode material4Ti5O12-TiO2The preparation method of the carbonized wing peel comprises the following steps: cleaning and drying the winged fruit peel, grinding the winged fruit peel into powder, soaking the powder in an activating agent solution, and magnetically stirring the powder for 4 hours at the temperature of 80 ℃; filtering, vacuum drying at 80 ℃ for 12h, calcining in a tube furnace at 700-900 ℃ for 1-3h under argon atmosphere, centrifugally washing the obtained product to neutrality by using hydrochloric acid and distilled water in sequence, vacuum drying at 80 ℃ for 12h, and grinding to obtain the target product carbonized wing peel.
Furthermore, the novel biomass carbon-coated dual-phase Li as the lithium ion battery cathode material4Ti5O12-TiO2And the activator solution is potassium hydroxide solution.
Furthermore, the novel biomass carbon-coated dual-phase Li as the lithium ion battery cathode material4Ti5O12-TiO2According to the mass ratio, the winged fruit peel is potassium hydroxide which is 1: 1-3.
Furthermore, the novel biomass carbon-coated dual-phase Li as the lithium ion battery cathode material4Ti5O12-TiO2The calcination temperature was 800 ℃.
Furthermore, the novel biomass carbon-coated dual-phase Li as the lithium ion battery cathode material4Ti5O12-TiO2The calcination temperature was 700 ℃.
Furthermore, the novel biomass carbon-coated dual-phase Li as the lithium ion battery cathode material4Ti5O12-TiO2The samara peel is derived from the samara of the Fraxinus chinensis.
The biomass carbon-coated biphase Li provided by the invention4Ti5O12-TiO2The lithium ion battery cathode material is applied to lithium ion batteries.
Further, the method is as follows: uniformly stirring a negative electrode material, a binder and a conductive agent, and coating the mixture on a copper foil to be used as a negative electrode of the lithium ion battery; the negative electrode material is the biomass carbon-coated biphase Li4Ti5O12-TiO2。
The invention has the beneficial effects that:
1. the material is easy to obtain, the micro-nano composite material is obtained by hydrothermal reaction in a reaction kettle, vacuum drying and high-temperature calcination, and the synthesis process conditions are simple to operate and easy to control, and industrial production is easy to realize.
2. The method takes the winged fruit peel of the natural plant ash tree as a carbon source, the main components of the winged fruit peel are cellulose, hemicellulose and lignin, the winged fruit peel is carbonized into functional carbon through high-temperature pyrolysis, the carbonization process is relatively simple, and the winged fruit peel has a unique micron-sized pore structure, so that the initial coulombic efficiency is higher. The fraxinus chinensis is widely distributed in the provinces of south and north China, and has the advantages of rich sources, environmental protection, sustainable regeneration and the like.
3. The invention relates to a method for preparing Chinese ash tree wing peel by mixing Chinese ash tree wing peel with binary Li4Ti5O12-TiO2The micro-nano composite material formed by the compound is applied to the lithium ion battery cathode material, and on one hand, the two-phase Li4Ti5O12-TiO2The nano composite structure increases the grain boundary density of a large interface area, and on the other hand, the micron-sized carbonized fin peel has a macroporous structure, so that a network-shaped support is formed for a product, a conductive network can be provided, and Li can be reduced4Ti5O12-TiO2The agglomeration of the carbon nanotubes increases the active sites of the reaction, improves the electronegativity of the material, and thus improves the electrochemical performance of the material. The micro-nano composite material not only has a special structure, but also comprises the characteristics of a micron material and the special performance of a nano material.
Drawings
FIG. 1 shows the fruit peel (a) and Li of the wings of Cera chinensis prepared by the present invention4Ti5O12-TiO2SE of-C composite (b)And (5) an M diagram.
FIG. 2 is an XRD pattern of the pericarp of the carbonized fraxinus chinensis prepared in the present invention.
FIG. 3 shows Li prepared by the present invention4Ti5O12-TiO2-XRD pattern of the C composite.
FIG. 4 shows the fruit peel (a) and Li of the wings of Cera chinensis prepared by the present invention4Ti5O12-TiO2-raman plot of C composite (b).
Detailed Description
The invention is further explained below with reference to specific embodiments, but is not intended to limit the scope of protection of the invention.
In order to improve the electrochemical performance of the lithium ion battery and find a suitable substitute of a negative electrode material lithium titanate, the invention provides a novel biomass carbon-coated biphase Li serving as a negative electrode material of the lithium ion battery4Ti5O12-TiO2The preparation method and the application thereof. The technical scheme is as follows:
preparation of biomass porous carbon material-carbonized ash tree wing pericarp
1) Dissolving potassium hydroxide in distilled water at room temperature to prepare a potassium hydroxide solution;
preferably, the concentration of the potassium hydroxide solution is 40-60 mg/mL.
More preferably, the concentration of the potassium hydroxide solution is 50 mg/mL.
2) Cleaning and drying the pterocarpus fraxinus pall peel, grinding into powder, soaking in a potassium hydroxide solution, and magnetically stirring for 4 hours at 80 ℃; filtering the treated fraxinus rhynchophylla pericarp powder, drying in vacuum at 80 ℃ for 12h, calcining in a tube furnace at 700-900 ℃ for 1-3h under argon atmosphere, centrifugally washing the obtained product to neutrality by using hydrochloric acid and distilled water in sequence, drying in vacuum at 80 ℃ for 12h, and grinding to obtain the target product carbonized fraxinus rhynchophylla pericarp.
Preferably, the ratio of the fraxinus rhynchophylla pericarp to the potassium hydroxide is 1:1-3 by mass ratio.
Preferably, the calcination temperature is 800 ℃ and the calcination time is 2 h.
Wherein potassium hydroxide solution is used asThe activating agent can introduce micropores and mesopores into a carbon skeleton of the biomass porous carbon, increase the pore volume of the micropores and the mesopores, and improve the specific surface area, thereby improving the performance in the aspects of energy storage and energy conversion. In the course of the reaction K+Can be embedded into carbon lattice of carbon skeleton to cause expansion of carbon lattice, and acid washing to remove K+And compounds thereof, such that a porous structure is formed.
(II) Biomass carbon-coated biphase Li4Ti5O12-TiO2Micro-nano composite material (Li)4Ti5O12-TiO2Preparation of-C)
1) Carbonizing the pericarp of the tree wing of Fraxinus chinensis and LiOH. H at room temperature2Ultrasonically dispersing O in deionized water, marking as a solution A, dispersing tetrabutyl titanate in an absolute ethyl alcohol solution, marking as a solution B, adding the solution A into the solution B, fully mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 12-36 h; and (3) centrifugally separating the precursor powder after the hydrothermal treatment, collecting the precipitate, performing cross centrifugal washing with distilled water and ethanol to neutrality, and performing vacuum drying at 80 ℃ for 24-36 h.
Preferably, the hydrothermal treatment temperature is 180 ℃ and the hydrothermal treatment time is 24 h.
2) Placing the precursor powder obtained in the step 1) in a tube furnace, calcining for 1-3h at the temperature of 600-800 ℃ in the argon atmosphere, and grinding to obtain a target product, namely the biomass carbon-coated dual-phase Li4Ti5O12-TiO2Micro-nano composite material, marked as Li4Ti5O12-TiO2-C。
Preferably, the calcination temperature is 700 ℃ and the calcination time is 2 h.
(III) lithium ion button cell
With Li4Ti5O12-TiO2And (3) taking the-C composite material as a negative electrode material, adding a proper amount of conductive agent and binder, uniformly mixing to form paste, uniformly coating the paste on copper foil to serve as a negative electrode, and taking a lithium sheet as a positive electrode to assemble the lithium ion battery.
Preferably, the conductive agent is acetylene black.
Preferably, the binder is PVDF.
Preferably, Li is present in a weight ratio4Ti5O12-TiO2And (3) a C composite material, namely acetylene black, PVDF (6-8), 1 and 3-1.
Example 1
Biomass carbon-coated biphase Li4Ti5O12-TiO2Micro-nano composite material (Li)4Ti5O12-TiO2-C), the preparation method is as follows:
1) grinding dried Alternaria serrata pericarp into powder, weighing 2.5g Alternaria serrata pericarp powder, adding into 50mL potassium hydroxide solution with concentration of 50mg/mL for activation, and magnetically stirring at 80 deg.C for 4 h. Filtering, and vacuum drying the activated Chinese ash samara peel powder at 80 deg.C for 12 h. Then placing the mixture into a tube furnace, calcining the mixture for 2 hours at 800 ℃ in an argon atmosphere, sequentially using hydrochloric acid and distilled water to centrifugally wash the obtained product to be neutral, drying the product for 12 hours in vacuum at 80 ℃, and grinding the product to obtain the target product carbonized fraxinus rhynchophylla pericarp.
2) Taking 0.04g of carbonized fraxinus chinensis pterocarpus fruit peel obtained in the step 1) and 0.168g of LiOH & H2Ultrasonically dispersing O in 30mL of deionized water, marking as a solution A, dispersing 1.7mL of tetrabutyl titanate in 25mL of absolute ethanol solution, marking as a solution B, adding the solution A into the solution B, fully stirring and uniformly mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours; centrifugally separating the precursor powder after hydrothermal treatment, collecting precipitate, alternately centrifugally washing the precipitate to be neutral by using distilled water and ethanol, carrying out vacuum drying for 24h at 80 ℃, finally placing the precipitate in a tube furnace, calcining for 2h at 700 ℃ in an argon atmosphere, and grinding to obtain a target product Li4Ti5O12-TiO2-a C composite material.
(II) characterization of the materials
FIG. 1 shows the fruit peel (a) and Li of the wings of Cera chinensis prepared by the present invention4Ti5O12-TiO2SEM picture of-C composite (b). As can be seen from a in FIG. 1, the carbonized fraxinus chinensis pterocarpus peel material prepared by the present invention has a macroporous structure of 1-2 μm. As can be seen from b in FIG. 1, Li prepared by the present invention4Ti5O12-TiO2-C composite material with micro-nano composite structure and nano-grade Li4Ti5O12-TiO2The biphase compound is embedded on the macroporous structure of the micron-sized biomass carbon. In addition, it can be seen that there are a large number of voids in the product, and due to the porous structure of the biomass, a network-like support is formed for the product, which not only can provide a conductive network, but also can reduce Li4Ti5O12、TiO2And (3) agglomeration.
Fig. 2 is an XRD chart of the prepared carbonized fraxinus pterocarpum pericarp, and it can be seen from fig. 2 that there is a distinct graphite type carbon characteristic peak at 2 θ ═ 26 °.
FIG. 3 shows Li prepared4Ti5O12-TiO2-XRD pattern of the C composite. As clearly observed from the figure, the prepared composite material has spinel type Li4Ti5O12Characteristic peak of (1) and rutile type TiO2The characteristic peak, the lower content of the biochar and the weaker diffraction intensity of the biochar lead to no obvious biochar diffraction peak in the XRD pattern of the composite material. Furthermore, Li4Ti5O12Diffraction peak of (3) and TiO2The diffraction peak of (A) is strong and sharp, indicating that Li is prepared4Ti5O12-TiO2the-C composite material has very high crystallinity, and the addition of the biochar has no influence on Li4Ti5O12And TiO2The structure of (1).
FIG. 4 shows the fruit peel (a) and Li of the wings of Cera chinensis prepared by the present invention4Ti5O12-TiO2-raman plot of C composite (b). As can be seen from FIG. 4, Li prepared by the present invention4Ti5O12-TiO2-C composite material at 1345cm-1、1588cm-1The existence of D peak and G peak proves the existence of carbon in the composite material, and the ratio R ═ I of the peak intensities of D band and G bandD/IGIs an important index reflecting the graphitization degree of the carbon layer. The smaller the R value, the higher the degree of graphitization of the carbon layer and the higher the degree of ordering of the carbon layer. Li prepared by the invention4Ti5O12-TiO2-C recombinationThe R value of the material was about 0.9, which indicates that Li4Ti5O12-TiO2The carbon layer in the-C composite material has higher graphitization degree, and the structure is favorable for improving the conductivity of the material.
The product prepared by the invention is Li by combining the drawings of 1, 2, 3 and 44Ti5O12、TiO2And biochar.
Example 2
Biomass carbon-coated biphase Li4Ti5O12-TiO2Micro-nano composite material (Li)4Ti5O12-TiO2-C), the preparation method is as follows:
1) grinding dried Alternaria serrata pericarp into powder, weighing 2.5g Alternaria serrata pericarp powder, adding into 50mL potassium hydroxide solution with concentration of 50mg/mL for activation, and magnetically stirring at 80 deg.C for 4 h. Filtering, and vacuum drying the activated Chinese ash samara peel powder at 80 deg.C for 12 h. Then placing the mixture into a tube furnace, calcining the mixture for 2 hours at 800 ℃ in an argon atmosphere, sequentially using hydrochloric acid and distilled water to centrifugally wash the obtained product to be neutral, drying the product for 12 hours in vacuum at 80 ℃, and grinding the product to obtain the target product carbonized fraxinus rhynchophylla pericarp.
2) Taking 0.05g of carbonized fraxinus chinensis pterocarpus fruit peel obtained in the step 1) and 0.168g of LiOH & H2Ultrasonically dispersing O in 30mL of deionized water, marking as a solution A, dispersing 1.7mL of tetrabutyl titanate in 25mL of absolute ethanol solution, marking as a solution B, adding the solution A into the solution B, fully stirring and uniformly mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours; centrifugally separating the precursor powder after hydrothermal treatment, collecting precipitate, alternately centrifugally washing the precipitate to be neutral by using distilled water and ethanol, carrying out vacuum drying for 24h at 80 ℃, finally placing the precipitate in a tube furnace, calcining for 2h at 700 ℃ in an argon atmosphere, and grinding to obtain a target product Li4Ti5O12-TiO2-a C composite material.
Example 3
Biomass carbon-coated biphase Li4Ti5O12-TiO2Micro-nano composite material (Li)4Ti5O12-TiO2-C), the preparation method is as follows:
1) grinding dried Alternaria serrata pericarp into powder, weighing 2.5g Alternaria serrata pericarp powder, adding into 50mL potassium hydroxide solution with concentration of 50mg/mL for activation, and magnetically stirring at 80 deg.C for 4 h. Filtering, and vacuum drying the activated Chinese ash samara peel powder at 80 deg.C for 12 h. Then placing the mixture into a tube furnace, calcining the mixture for 2 hours at 800 ℃ in an argon atmosphere, sequentially using hydrochloric acid and distilled water to centrifugally wash the obtained product to be neutral, drying the product for 12 hours in vacuum at 80 ℃, and grinding the product to obtain the target product carbonized fraxinus rhynchophylla pericarp.
2) Taking 0.06g of the carbonized fraxinus chinensis pterocarpus fruit skin obtained in the step 1) and 0.168g of LiOH. H2Ultrasonically dispersing O in 30mL of deionized water, marking as a solution A, dispersing 1.7mL of tetrabutyl titanate in 25mL of absolute ethanol solution, marking as a solution B, adding the solution A into the solution B, fully stirring and uniformly mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 24 hours; centrifugally separating the precursor powder after hydrothermal treatment, collecting precipitate, alternately centrifugally washing the precipitate to be neutral by using distilled water and ethanol, carrying out vacuum drying for 24h at 80 ℃, finally placing the precipitate in a tube furnace, calcining for 2h at 700 ℃ in an argon atmosphere, and grinding to obtain a target product Li4Ti5O12-TiO2-a C composite material.
Example 4
Biomass carbon-coated biphase Li4Ti5O12-TiO2Application of negative electrode material in lithium ion battery
The method for assembling the lithium ion battery comprises the following steps: li prepared in examples 1, 2 and 3, respectively, using commercially available acetylene black as the conductive agent material and PVDF as the binder4Ti5O12-TiO2-C as a negative electrode material, in mass ratio, Li4Ti5O12-TiO2And (3) mixing and pasting an-C composite material, namely acetylene black and PVDF, uniformly coating the mixture on copper foil to serve as a negative electrode, and taking a lithium sheet as a positive electrode to respectively assemble the composite material into button cells.
And (3) electrochemical performance testing:
commercially available Li4Ti5O12The material was used as a battery negative electrode material and a lithium plate was used as a counter electrode to assemble a button cell, which was used as a comparative example, and electrochemical performance tests were performed, and the results are shown in table 1.
TABLE 1 comparison of electrochemical Performance of batteries made with different cathode materials (Charge and discharge multiplying factor 1C)
As can be seen from Table 1, compared with ordinary Li4Ti5O12Cathode material, Li synthesized by the method of the invention4Ti5O12-TiO2the-C composite material has better electrochemical performance. With the increase of the quality of the biomass carbon, the electrochemical performance of the composite material synthesized by the method of the invention is firstly increased and then weakened, and it can be seen that the electrochemical performance of the composite material obtained by adding 0.05g of biomass carbon in the example 2 and calcining is obviously higher than that of the composite materials in the examples 1 and 3. And the raw material adopts natural Chinese ash tree wing pericarp, is green and environment-friendly and is easy to obtain. Li synthesized by the method of the present invention4Ti5O12-TiO2the-C composite material shows good cycling stability in 100 charge-discharge cycles. On the one hand, the two-phase Li keeps the excellent characteristics of LTO4Ti5O12-TiO2The nano composite structure increases the grain boundary density of a large interface area, and on the other hand, the micron-sized carbonized fin peel has a macroporous structure, so that a network-shaped support is formed for a product, a conductive network can be provided, and Li can be reduced4Ti5O12、TiO2The agglomeration of the carbon nanotubes increases the active sites of the reaction, improves the electronegativity of the material, and thus improves the electrochemical performance of the material. The invention adopts an extremely simple hydrothermal method for one-step synthesis, and is beneficial to realizing commercialization of the LTO cathode material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. Novel biomass carbon-coated biphase Li serving as lithium ion battery negative electrode material4Ti5O12-TiO2The preparation method is characterized by comprising the following steps: mixing carbonized wing peel with LiOH. H2Ultrasonically dispersing O in deionized water, marking as a solution A, dispersing tetrabutyl titanate in an absolute ethyl alcohol solution, marking as a solution B, adding the solution A into the solution B, fully stirring and mixing, transferring to a stainless steel reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 12-36 h; collecting the precursor powder after the hydrothermal treatment, cross-washing the precursor powder to be neutral by using distilled water and ethanol, drying the precursor powder for 24 to 36 hours in vacuum at the temperature of 80 ℃, then placing the dried precursor powder in a tubular furnace, calcining the dried precursor powder for 1 to 3 hours at the temperature of 600-800 ℃ in the argon atmosphere, and grinding the calcined precursor powder to obtain a target product, namely the biomass carbon-coated dual-phase Li4Ti5O12-TiO2A composite material.
2. The novel biomass carbon-coated dual-phase Li as anode material of lithium ion battery as claimed in claim 14Ti5O12-TiO2The method for preparing the carbonized fin peel is characterized by comprising the following steps: cleaning and drying the winged fruit peel, grinding the winged fruit peel into powder, soaking the powder in an activating agent solution, and magnetically stirring the powder for 4 hours at the temperature of 80 ℃; filtering, vacuum drying at 80 ℃ for 12h, calcining in a tube furnace at 700-900 ℃ for 1-3h under argon atmosphere, centrifugally washing the obtained product to neutrality by using hydrochloric acid and distilled water in sequence, vacuum drying at 80 ℃ for 12h, and grinding to obtain the target product carbonized wing peel.
3. The novel biomass carbon-coated dual-phase Li as anode material of lithium ion battery as claimed in claim 24Ti5O12-TiO2The method is characterized in that the activator solution is a potassium hydroxide solution.
4. A new form as claimed in claim 3Biomass carbon-coated biphase Li serving as negative electrode material of lithium ion battery4Ti5O12-TiO2The method is characterized in that the weight ratio of the winged fruit peel to potassium hydroxide is 1: 1-3.
5. The novel biomass carbon-coated dual-phase Li as anode material of lithium ion battery as claimed in claim 24Ti5O12-TiO2Characterized in that the calcination temperature is 800 ℃.
6. The novel biomass carbon-coated dual-phase Li as anode material of lithium ion battery as claimed in claim 14Ti5O12-TiO2Characterized in that the calcination temperature is 700 ℃.
7. The novel biomass carbon-coated dual-phase Li of the anode material of the lithium ion battery as claimed in any one of claims 1 to 64Ti5O12-TiO2The method is characterized in that the winged fruit peel is derived from the pterocarpus heterophyllus.
8. Biomass carbon-coated biphasic Li prepared by the method of any one of claims 1-64Ti5O12-TiO2The lithium ion battery cathode material is applied to lithium ion batteries.
9. Use according to claim 8, characterized in that the method is as follows: uniformly stirring a negative electrode material, a binder and a conductive agent, and coating the mixture on a copper foil to be used as a negative electrode of the lithium ion battery; the negative electrode material is biomass carbon-coated dual-phase Li prepared by the method of any one of claims 1 to 64Ti5O12-TiO2。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324511A (en) * | 2011-10-09 | 2012-01-18 | 北京科技大学 | Preparation method for lithium ion battery composite cathode material |
| CN104638255A (en) * | 2015-02-02 | 2015-05-20 | 斌源材料科技（上海）有限公司 | Lithium titanate/carbon composite material and method for preparing material |
| CN106816593A (en) * | 2017-03-03 | 2017-06-09 | 辽宁大学 | A kind of lithium ion battery negative material Li4Ti5O12/TiO2Nano-chip arrays and its preparation method and application |
| CN106848251A (en) * | 2017-03-15 | 2017-06-13 | 北京朗盛特耐科技有限公司 | A kind of preparation method of CNT lithium titanate composite anode material |
| CN111268677A (en) * | 2020-01-20 | 2020-06-12 | 辽宁大学 | Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324511A (en) * | 2011-10-09 | 2012-01-18 | 北京科技大学 | Preparation method for lithium ion battery composite cathode material |
| CN104638255A (en) * | 2015-02-02 | 2015-05-20 | 斌源材料科技（上海）有限公司 | Lithium titanate/carbon composite material and method for preparing material |
| CN106816593A (en) * | 2017-03-03 | 2017-06-09 | 辽宁大学 | A kind of lithium ion battery negative material Li4Ti5O12/TiO2Nano-chip arrays and its preparation method and application |
| CN106848251A (en) * | 2017-03-15 | 2017-06-13 | 北京朗盛特耐科技有限公司 | A kind of preparation method of CNT lithium titanate composite anode material |
| CN111268677A (en) * | 2020-01-20 | 2020-06-12 | 辽宁大学 | Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed |
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