CN114975953B - Cerium-containing battery negative electrode material and preparation method thereof - Google Patents
Cerium-containing battery negative electrode material and preparation method thereof Download PDFInfo
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- CN114975953B CN114975953B CN202210700409.9A CN202210700409A CN114975953B CN 114975953 B CN114975953 B CN 114975953B CN 202210700409 A CN202210700409 A CN 202210700409A CN 114975953 B CN114975953 B CN 114975953B
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 53
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 title claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 33
- 239000010405 anode material Substances 0.000 claims abstract description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 5
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- -1 modified lithium titanate Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 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 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
-
- 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 cerium-containing battery anode material, which is prepared from carbides of cerium-containing titanium dioxide nano particles and lithium carbonate by a high-temperature solid-phase method. In addition, the preparation method of the cerium-containing battery anode material is also disclosed. Compared with the prior art, the cerium-containing battery anode material has higher discharge capacity, better rate capability and more stable cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and relates to a cerium-containing battery negative electrode material and a preparation method thereof.
Background
Batteries can be used completely independently and do not require the input or output of any chemicals, battery technology is considered an important solution to the energy crisis, alleviating the growing energy demands and the increasingly severe environmental problems.
In the battery technology, the lithium ion battery is widely used in various mobile equipment because of the advantages of long service life, high energy density, quick charge and discharge, no memory effect, no pollution to the environment and the like, and is widely applied to various industries such as mobile phones, electric automobiles, electric toys, communication base stations, satellites, airships, underwater robots and the like.
The lithium ion battery mainly comprises a positive electrode material and a negative electrode material which can perform reversible deintercalation reaction, an electrolyte capable of transmitting lithium ions and a diaphragm. During charging, lithium ions are separated from an anode active material under the drive of external voltage, migrate to a cathode through an electrolyte and are embedded into the cathode active material, meanwhile, electrons flow from the anode to the cathode through an external circuit, and the battery realizes conversion of electric energy into chemical energy in a high-energy state of lithium enrichment and lithium poor in the cathode; during discharge, lithium ions are deintercalated from the negative electrode and migrate to the lattice of the active substance after being embedded into the positive electrode, electrons in an external circuit flow from the negative electrode to the positive electrode to form current, and the conversion from chemical energy to electric energy is realized.
Improvement of lithium ion batteries is important for development of mobile devices and the like, and a negative electrode material of the lithium ion batteries is one of key factors limiting the capacity of the lithium ion batteries. Since the lithium ion battery was invented to date, the negative electrode material of the lithium ion battery has been replaced by carbon material (mainly graphite material), silicon-based material, tin-based material, alloy material, metal oxide material, etc.
The recycling and safety of graphite materials has been greatly developed and improved, but there are still a number of disadvantages: the first charge and discharge capacity is generally low, the synthetic route is complex, and dendrite-initiated safety problems and the like are easy to generate. Compared with other cathode materials, spinel-type lithium titanate has been studied by a large number of energy workers because of its advantages of zero strain. The zero strain is that the volume and lattice constant change of the fingertip spinel type lithium titanate material in the phase change process are very small. Spinel type lithium titanate Li 4 Ti 5 O 12 Belongs to a face-centered cubic structure, has good cycle performance, higher charge-discharge platform and high lithium ion diffusion coefficient.
In general, the properties of the materials prepared are seriously affected by the difference in the preparation methods. The traditional preparation method of spinel type lithium titanate mainly comprises a high-temperature solid-phase reaction method, a liquid-phase method and an electrostatic spinning method. The preparation method has great influence on improving the microstructure and electrochemical performance of the anode material, and different preparation methods can lead the prepared compound to have different performances in the aspects of structure, specific surface area, morphology, color, electrochemical property and the like.
Chinese patent application publication CN110880593a discloses a solid electrolyte modified lithium titanate negative electrode material and a preparation method thereof, and the microstructure of the lithium titanate negative electrode material is as follows: the secondary particles are spherical and have a particle diameter of 5-20 mu m, and consist of primary particles with a grain size of 20-200 nm; the surface of lithium titanate particles in the lithium titanate negative electrode material is attachedA lithium ion solid electrolyte composed of fluorine-containing oxide and fluoride, wherein the mass fraction of the lithium ion solid electrolyte is 0.1-3%; the preparation method comprises the following steps: one or more fluorine-containing lithium battery electrolyte, titanium dioxide and lithium salt are subjected to twice sanding, twice spray granulation and twice solid-phase calcination to obtain the fluorine-containing lithium battery electrolyte. The tap density of the prepared lithium titanate anode material reaches 1.3g/cm 3 The pH value is 8-10, the rate performance is good, and the 5C discharge capacity reaches 135 mAh.g -1 The above.
Chinese patent application publication CN102969491a discloses a method for preparing negative electrode material lithium titanate for lithium battery, which is characterized in that: the process flow comprises the following steps: 1) Slowly dissolving a certain amount of titanyl sulfate; preparing 10% -25% aqueous solution in deionized water for 3-28 hr, controlling water temperature at 25-70deg.C, filtering the dissolved solution to remove impurities, and clarifying and transparency; 2) Adding lithium hydroxide into a titanyl sulfate solution according to the mole ratio of Li to Ti=1.16:1, and adding a stabilizer; selected from polyhydroxy aldehyde, organic amine, polyhydric alcohol, aldehyde and organic acid, and the addition amount is 0.3-0.8%; reacting for 2-5 hours at 50-90 ℃ and pH of 2-6 to form sol; 3) Drying the sol in a vacuum oven at 60-100 ℃ for one night to obtain dry powder, grinding the dry powder, and preparing the dry powder for burning; 4) The ground dry powder is calcined in a high-temperature section way, and calcined at 700-900 ℃ in a high-temperature furnace for 10-20 hours, so as to obtain the spinel-structured lithium titanate sample.
Chinese patent application publication CN104037395a discloses a method for preparing a graphene-polypyrrole-lithium titanate composite lithium battery negative electrode material. Firstly, preparing a mixed solution a of pyrrole monomers and graphene, adding lithium titanate into the mixed solution a, uniformly dispersing to obtain a mixed solution b, adding an initiator into the mixed solution b to polymerize the pyrrole monomers into polypyrrole, filtering, washing and finally baking to obtain the polymer. The polypyrrole is combined with the graphene and the lithium titanate, the graphene coating layer on the surface of the lithium titanate of the obtained composite anode material is relatively compact, the contact resistance between materials can be greatly reduced, the conductivity and the electrochemical performance of the material are obviously improved, and compared with the traditional carbon coating method, the composite anode material does not needHigh-temperature calcination, no introduction of reducing atmosphere, and avoidance of Ti in lithium titanate 4+ Thereby greatly improving the multiplying power performance and the safety performance of the battery, and having the advantages of energy conservation and environmental protection and simple process.
Chinese patent application publication CN108682805a discloses a method for preparing porous nanofiber by combining electrostatic spinning with sol-gel method, comprising the following steps: step one: preparing a carbon nano tube doped lithium titanate sol precursor; step two: preparing an electrospinning precursor solution; step three: preparing a lithium titanate nanowire precursor through electrostatic spinning; step four: preparing the doped lithium titanate-carbon composite nanofiber at a high temperature. The method prepares the carbon nanotube doped porous lithium titanate nanofiber by utilizing a sol-gel combined electrospinning technology, and overcomes the defects of lithium titanate by three means of doping, porous and nanofiber, so that the performance of the material is optimized.
However, the prior art still has the technical defects of poor electrochemical performance, especially poor discharge capacity, rate capability and cycle performance of lithium titanate. Therefore, there is an urgent need to provide a cerium-containing battery negative electrode material with better discharge capacity, rate capability and cycle performance, and a preparation method thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cerium-containing battery anode material with better discharge capacity, rate capability and cycle performance and a preparation method thereof.
In order to achieve the above object, on the one hand, the technical scheme adopted by the invention is as follows: the negative electrode material of the cerium-containing battery is characterized in that the negative electrode material is prepared from carbide containing cerium-containing titanium dioxide nano particles and lithium carbonate by a high-temperature solid phase method.
The negative electrode material according to the present invention, wherein the molar ratio of (Ti+Ce) atoms to Li atoms in the carbide of the cerium-containing titanium dioxide nanoparticles is 5 (4.1 to 4.5).
The negative electrode material according to the present invention, wherein the molar ratio of Ti atoms to Ce atoms in the carbide of the cerium-containing titanium dioxide nanoparticles is 1 (0.06-0.07).
The anode material according to the present invention, wherein the carbon content of the anode material is 3.2 to 5.2wt%.
The negative electrode material of the invention, wherein the high-temperature solid phase method is as follows: the reaction temperature is 750-850 ℃, and the reaction time is 6-16h.
The negative electrode material according to the present invention, wherein the carbide of the cerium-containing titanium oxide nanoparticle has a carbon content of 4.0 to 8.0wt%.
The anode material according to the present invention, wherein the anode material has an average particle diameter of 100 to 300nm.
The negative electrode material according to the present invention, wherein the average particle diameter of the cerium-containing titanium dioxide nanoparticles is 20 to 60nm.
The negative electrode material according to the present invention, wherein the cerium-containing titanium dioxide nanoparticles have an anatase type titanium dioxide crystal structure.
In another aspect, the present invention also provides a method for preparing the negative electrode material for a cerium-containing battery according to the present invention, characterized in that,
preparing cerium-containing titanium dioxide nano particles by a sol-gel method, and burning for 2-8 hours at 550-650 ℃;
based on the weight of the cerium-containing titanium dioxide nano-particles, adding 10-20wt% of polyvinyl alcohol with the average polymerization degree of 1700-1800, uniformly mixing, and reacting at 650-750 ℃ for 0.5-4h to obtain carbides of the cerium-containing titanium dioxide nano-particles;
and uniformly mixing the carbide of the cerium-containing titanium dioxide nano particles with lithium carbonate, and performing a high-temperature solid-phase reaction to obtain the cerium-containing battery anode material.
Compared with the prior art, the cathode material of the cerium-containing battery has higher discharge capacity, better rate capability and more stable cycle performance.
Detailed Description
It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both a reference and a plurality of references (i.e., more than two, including two) unless the context clearly dictates otherwise.
Unless otherwise indicated, the numerical ranges in the present invention are approximate, and thus values outside the ranges may be included. The numerical ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will also be understood that the endpoints of each of the numerical ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
References in the specification and the claims to parts by weight of a particular element or component in a composition or article refer to the relationship by weight between that element or component and any other element or component in the composition or article.
In the present invention, unless specifically indicated to the contrary, or implied by the context of the context or conventional means in the art, the solutions referred to in the present invention are aqueous solutions; when the solute of the aqueous solution is a liquid, all fractions and percentages are by volume, and the volume percent of the component is based on the total volume of the composition or product comprising the component; when the solute of the aqueous solution is a solid, all fractions and percentages are by weight, and the weight percentages of the components are based on the total weight of the composition or product comprising the components.
References to "comprising," "including," "having," and similar terms in this invention are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials. In contrast, the term "consisting of … …" excludes any component, step or procedure not specifically recited or enumerated. The term "or" refers to members recited individually as well as in any combination unless otherwise specified.
Furthermore, the contents of any of the referenced patent documents or non-patent documents in the present invention are incorporated by reference in their entirety, especially with respect to the definitions and general knowledge disclosed in the art (in case of not inconsistent with any definitions specifically provided by the present invention).
In the present invention, parts are parts by weight unless otherwise indicated, temperatures are expressed in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. Room temperature represents 20-30 ℃. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, solvents needed, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
10.2g (30 mmol) of tetrabutyl titanate was stirred and mixed with 10mL of absolute ethanol to obtain an ethanol solution of titanate. 0.83g (1.9 mmol) of cerium nitrate hexahydrate was dissolved in 80mL of absolute ethanol: and adding acetic acid into the mixed solvent with the water volume ratio of=4:1 to adjust the pH value to be=2.0, so as to obtain the cerium nitrate solution. And (3) dropwise adding the ethanol solution of the titanate into the cerium nitrate solution at the speed of 1mL/min, and continuing stirring and reacting for 6h after the dropwise adding is finished. And standing for 24 hours after the reaction is finished. Drying at 120deg.C for 3 hr, and grinding into powder. And firing for 5 hours at 600 ℃ to obtain the cerium-containing titanium dioxide nano particles.
According to SEM image statistics, the average particle size of the cerium-containing titanium dioxide nanoparticles is 45+ -8 nm. The XRD patterns showed diffraction peaks of crystal planes of anatase titania (101), (104), (200), (105), (211), (204), (116), (220), (125) and (303), etc., but no diffraction peak of visible ceria crystals was observed.
Example 2
Based on the weight of the cerium-containing titanium dioxide nanoparticles of example 1, 15wt% of polyvinyl alcohol PVA1750 was added, then a proper amount of absolute ethyl alcohol was added, stirred to be uniformly mixed, and then the absolute ethyl alcohol was distilled off under reduced pressure to obtain a mixture. And (3) heating the mixture from room temperature to 700 ℃ at a speed of 2 ℃/min in nitrogen atmosphere, keeping the temperature for 1h at a constant temperature, and naturally cooling to room temperature to obtain the carbide containing cerium-containing titanium dioxide nano particles. The carbon content of the carbide of the cerium-containing titanium dioxide nanoparticles was 6.2% by thermal weight loss analysis.
Example 3
The carbide of the cerium-containing titanium dioxide nanoparticle of example 2 is uniformly mixed with 2.0g of lithium carbonate, the temperature is raised to 800 ℃ from room temperature at a speed of 2 ℃/min in nitrogen atmosphere, the constant temperature is maintained for 10 hours, and the temperature is naturally lowered to room temperature, so that the cerium-containing lithium titanate nanomaterial is obtained. According to SEM image statistics, the average particle size of the cerium-containing lithium titanate nano material is 170+/-32 nm. The carbon content of the cerium-containing lithium titanate nanomaterial was 4.3% by thermal weight loss analysis.
Comparative example 1
Example 1 titanium dioxide nanoparticles were obtained without addition of cerium nitrate hexahydrate. On this basis, a carbide of titanium dioxide nanoparticles was prepared as in example 2, and then uniformly mixed with 1.9g of lithium carbonate, and then a lithium titanate nanomaterial was prepared as in example 3.
Comparative example 2
The cerium-containing titanium oxide nanoparticle of example 1 was directly and uniformly mixed with 2.0g of lithium carbonate without the process of example 2, and then a cerium-containing lithium titanate nanomaterial was prepared according to the process of example 3.
Electrochemical performance test
Mixing a lithium titanate nano material or a cerium-containing lithium titanate nano material, conductive carbon black (carbon VVC 72) and a binder polyvinylidene fluoride (PVDF) according to the weight ratio of 80:10:10 to form electrode slurry, coating the electrode slurry on a copper foil by using a film coater to form a film with the thickness of about 100 mu m, drying the film at 120 ℃ for 3 hours, and compacting the film at the pressure of 20MPa to form the electrode film. Finally, the electrode membrane is dried for 24 hours at 120 ℃ in a vacuum drying oven and then punched into a round electrode slice with the diameter of 13 mm. The round pole piece is a working electrode, and the counter electrode and the reference electrode are lithium pieces with phi 17mm multiplied by 0.5 mm.
The separator was a Celgard 2400 polypropylene film manufactured by Celgard corporation of America, cut into round separator of phi 20mm with a sheet punching machine, and placed one sheet between the working electrode and the lithium sheet when the coin cell was assembled.
The electrolyte is 1M LiPF 6 Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) (moisture content below 200ppm, wherein EC: DMC: emc=1:1:1 (weight ratio).
In the experiment, the electrochemical performance of the battery is tested by adopting an R2430 button simulation battery, and the battery assembling process is carried out in a dry glove box protected by high-purity argon. The analog battery is charged/discharged by adopting a constant current mode, the charge/discharge position is controlled within the range of 1-3, and the current density is controlled at 0.1C (17.5 mA.g) -1 ) And 5C, recording the specific capacity of the first discharge (mAh.g -1 ) Discharge capacity retention (%) after 150 cycles under 5C discharge conditions. The results are shown in Table 1.
TABLE 1
| Specific discharge capacity of 0.1C | Specific discharge capacity of 5C | Discharge capacity retention rate | |
| Example 3 | 324.6 | 145.9 | 98.3 |
| Comparative example 1 | 281.3 | 86.5 | 94.2 |
| Comparative example 2 | 253.9 | 125.7 | 95.0 |
As can be seen from table 1, the product of the example of the present invention has a higher discharge capacity, better rate performance, and more stable cycle performance than comparative examples 1-2.
Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.
Claims (5)
1. The negative electrode material of the cerium-containing battery is characterized in that the negative electrode material is prepared from carbide containing cerium-containing titanium dioxide nano particles and lithium carbonate by a high-temperature solid phase method;
wherein, the molar ratio of (Ti+Ce) atoms to Li atoms in the carbide of the cerium-containing titanium dioxide nano particles is 5 (4.1-4.5);
the molar ratio of Ti atoms to Ce atoms in the carbide of the cerium-containing titanium dioxide nano particles is 1 (0.06-0.07);
the carbon content of the anode material is 3.2-5.2wt%;
the preparation method of the anode material comprises the following steps:
preparing cerium-containing titanium dioxide nano particles by a sol-gel method, and burning for 2-8 hours at 550-650 ℃;
based on the weight of the cerium-containing titanium dioxide nano-particles, adding 10-20wt% of polyvinyl alcohol with the average polymerization degree of 1700-1800, uniformly mixing, and reacting at 650-750 ℃ for 0.5-4h to obtain carbides of the cerium-containing titanium dioxide nano-particles;
uniformly mixing the carbide of the cerium-containing titanium dioxide nano particles with lithium carbonate, and performing a high-temperature solid-phase reaction to obtain a cerium-containing battery anode material;
the high-temperature solid phase method comprises the following steps: the reaction temperature is 750-850 ℃ and the reaction time is 6-16h;
the carbon content of the carbide of the cerium-containing titanium dioxide nano-particles is 4.0-8.0wt%.
2. The anode material according to claim 1, wherein an average particle diameter of the anode material is 100-300nm.
3. The negative electrode material according to claim 1, wherein the average particle diameter of the cerium-containing titanium oxide nanoparticles is 20 to 60nm.
4. The negative electrode material of claim 1, wherein the cerium-containing titanium dioxide nanoparticles are of anatase titanium dioxide crystal structure.
5. A method for producing the negative electrode material for a cerium-containing battery according to any one of claims 1 to 4, characterized in that,
preparing cerium-containing titanium dioxide nano particles by a sol-gel method, and burning for 2-8 hours at 550-650 ℃;
based on the weight of the cerium-containing titanium dioxide nano-particles, adding 10-20wt% of polyvinyl alcohol with the average polymerization degree of 1700-1800, uniformly mixing, and reacting at 650-750 ℃ for 0.5-4h to obtain carbides of the cerium-containing titanium dioxide nano-particles;
and uniformly mixing the carbide of the cerium-containing titanium dioxide nano particles with lithium carbonate, and performing a high-temperature solid-phase reaction to obtain the cerium-containing battery anode material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376937A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院金属研究所 | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof |
| CN104253267A (en) * | 2013-06-27 | 2014-12-31 | 上海电气集团股份有限公司 | Carbon-clad spinel lithium titanate material, production method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376937A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院金属研究所 | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof |
| CN104253267A (en) * | 2013-06-27 | 2014-12-31 | 上海电气集团股份有限公司 | Carbon-clad spinel lithium titanate material, production method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 国家标准化管理委员会.中华人民共和国国家标准-锂离子电池用钛酸锂及其炭复合负极材料.2015,第1-15页. * |
| 连芳.电化学储能器件及关键材料.冶金工业出版社,2019,第138-139页. * |
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