CN112838204A - Negative electrode active material, preparation method thereof, negative electrode material, negative electrode sheet and battery - Google Patents
Negative electrode active material, preparation method thereof, negative electrode material, negative electrode sheet and battery Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 13
- 229910052810 boron oxide Inorganic materials 0.000 claims description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 239000006183 anode active material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229940119177 germanium dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 29
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000007578 melt-quenching technique Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- H01M4/48—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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 application discloses a negative electrode active material, a preparation method thereof, a negative electrode sheet and a battery. The negative electrode active material includes amorphous vanadium pentoxide as a negative electrode active material main body. The negative electrode active material according to the embodiment of the present application has at least the following advantageous effects: crystal V2O5V in2O5The structural unit has a layered structure to provide a proper interlayer distance for intercalation reaction, the layered structure of the material can not be changed after lithium ions are embedded, and the embedding and extracting processes are completely reversible, so that the lithium ion battery has high output voltage. The applicant has surprisingly found that after it is prepared as an amorphous material, V2O5The layered structure of (a) still exists, and the formed further open lithium ion diffusion channel can allow more lithium ionsThe son can be reversibly inserted and extracted, so that the specific capacity is higher; amorphous V2O5The characteristic of the crystal-free interface enables the structure of the material to be more stable in the charging and discharging process, and the cycle life is greatly prolonged.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a negative electrode active material, a preparation method thereof, a negative electrode material, a negative electrode sheet and a battery.
Background
The main structure of the lithium ion battery comprises a positive electrode, a negative electrode, an electrolyte, a diaphragm and the like, wherein the positive electrode and the negative electrode are generally compound materials capable of reversibly inserting or extracting lithium ions. During charging, lithium ions are extracted from the positive electrode material and are inserted into the negative electrode material through the electrolyte and the diaphragm, so that the positive electrode active material is in a lithium-poor state; during battery discharge, lithium ions are extracted from the negative electrode material and re-inserted into the positive electrode material through the electrolyte and the separator, so that the positive electrode material is in a lithium-rich state. In order to keep the charge balance, electrons with the same number in the charge-discharge process are cooperated with lithium ion migration through an external circuit to move back and forth between the positive electrode and the negative electrode, so that the positive electrode and the negative electrode generate corresponding redox reactions. Moreover, the lithium ions have relatively fixed spatial positions in the positive electrode and the negative electrode, so that the reversibility of the lithium ion battery is good, and the service life and the safety of the battery are ensured.
However, with the widespread use of portable electronic devices and electric vehicles, the demand for the performance of lithium ion batteries is increasing. The negative electrode is a carrier for storing lithium of the lithium ion battery, and the selection of different negative electrode materials can change the first charge-discharge efficiency, the cycle performance and the like of the lithium ion battery, so that the overall performance of the lithium ion battery is directly influenced. The current research on negative electrode active materials has mainly focused on crystalline materials, such as graphite negative electrodes, lithium titanate negative electrodes, silicon negative electrodes, and the like, but recent years of research have shown that the electrochemical performance of crystalline negative electrode active materials has been approaching to the limit and is difficult to be further improved. The theoretical specific capacity of the active material of the crystal graphite cathode used in the commercial battery is lower and is only 372 mAh/g; although the crystalline silicon negative electrode which is considered as the next generation commercial negative electrode active material has a high specific capacity of 4200mAh/g, a series of problems such as capacity reduction, structural collapse, electrode failure and the like are generated due to huge volume change (-400%) in the circulation process, so that the circulation stability of the crystalline silicon negative electrode cannot be ensured, and the crystalline silicon negative electrode is difficult to popularize and apply on a large scale.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides a negative electrode active material with good specific capacity and cycling stability, a preparation method thereof, a negative electrode material, a negative electrode piece and a battery.
In a first aspect of the present application, there is provided an anode active material including amorphous vanadium pentoxide as an anode active material main body.
The negative electrode active material according to the embodiment of the present application has at least the following advantageous effects:
crystal V2O5V in2O5The structural unit has a layered structure to provide a proper interlayer distance for intercalation reaction, the layered structure of the material can not be changed after lithium ions are embedded, and the embedding and extracting processes are completely reversible, so that the lithium ion battery has high output voltage. The applicant has surprisingly found that after it is prepared as an amorphous material, V2O5The formed further open lithium ion diffusion channel can allow more lithium ions to be reversibly inserted and extracted, so that the lithium ion diffusion channel has higher specific capacity; amorphous V2O5The characteristic of the crystal-free interface enables the structure of the material to be more stable in the charging and discharging process, and the cycle life is greatly prolonged.
Wherein the negative electrode active material main body means amorphous vanadium pentoxide having a content of at least 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% or more based on the total mass of the negative electrode active material.
According to some embodiments of the present application, amorphous vanadium pentoxide has a network forming body oxide co-fused therein. The cost of forming an amorphous material by using the single vanadium pentoxide is higher, such as by magnetron sputtering, deposition, sol-gel and other methods, the amorphous of the vanadium pentoxide can be promoted by fusing a network forming body oxide in the material, a glass cathode active substance can be more easily formed, and meanwhile, the material structure of the amorphous vanadium pentoxide can be effectively stabilized, so that the method can be suitable for industrial large-scale production with lower production cost.
According to some embodiments of the present application, the network forming body oxide is selected from boron oxide, silicon dioxide, phosphorus pentoxide, germanium dioxide, tin dioxide, and the like. The oxide can be independently formed into a glassy state, and can be used as a network former oxide.
According to some embodiments of the application, the network forming body oxide is boron oxide.
According to some embodiments of the present application, in the anode active material, a molar ratio of the amorphous vanadium pentoxide to the network formation body oxide is not less than 3: 2. the reversible embedding and releasing of the negative active material are realized mainly by amorphous vanadium pentoxide, so that the smaller the content of the oxide of the network forming body, the more favorable the electrochemical properties such as the cycle performance, the specific capacity and the like of the battery are.
According to some embodiments of the present application, the negative active material has an X-ray diffraction spectrum having an amorphous peak within 20 DEG 2 theta 30 deg.
In a second aspect of the present application, there is provided a method for producing an anode active material, the method comprising the steps of:
the method comprises the following steps: uniformly mixing the oxide of the network forming body or the precursor thereof and vanadium pentoxide to obtain a mixed material;
step two: and melting the mixed material, quenching and annealing the molten product to obtain the negative active material.
According to the preparation method of the negative electrode active material, at least the following beneficial effects are achieved:
vanadium pentoxide and network forming body oxide or precursor thereof are used as raw materials to prepare the negative active material, and the raw materials are low in price and wide in source. Meanwhile, the melting-quenching preparation method is simple, easy to learn and short in period, and meets the industrial production conditions.
The network-forming oxide or a precursor thereof is a substance containing the network-forming oxide or capable of reacting to form the network-forming oxide during melt quenching or the like. Specifically, for example, as for boron oxide, boric acid can be used as a precursor thereof, and boric acid forms boron oxide under high-temperature melt reaction conditions; for example, for phosphorus pentoxide, ammonium phosphate can be used as its precursor, which forms phosphorus pentoxide under high temperature melt reaction conditions.
According to some embodiments of the present application, the first step is specifically: and mixing and ball-milling the network forming body oxide or the precursor thereof, vanadium pentoxide and a grinding aid, and filtering and drying the ball-milled product to obtain a mixed material. Through the use of the grinding aid, the materials can be prevented from agglomerating in the ball milling process, and the materials can be mixed more uniformly.
According to some embodiments of the present application, in the second step, the melting temperature is 1000-1100 ℃, and the holding time is 1-2 hours. Melting temperature and holding time for V in the final product4+And V5+The ratio of these two ions has an important influence, and the ratio of these two ions directly affects the electrochemical properties of the negative active material and ultimately changes the battery performance. When the melting temperature is controlled to be 1000-1100 ℃ and the heat preservation time is controlled to be 1-2 h, the cathode active material shows excellent electrochemical properties.
According to some embodiments of the present application, in the second step, the annealing temperature is 300 to 350 ℃. When the amorphous material is prepared by a melt quenching method, annealing treatment is generally performed at a temperature below the glass transition temperature. The annealing temperature of the embodiment of the application is 30-80 ℃ higher than the glass transition temperature (Tg) of an actual product, and compared with the common annealing temperature, the negative active material formed by the method has better electrochemical performance.
According to some embodiments of the present application, in step one, both the vanadium pentoxide and the network former oxide or precursor thereof have a purity greater than 99.5%.
According to some embodiments of the present application, the grinding aid in the first step is an organic solvent such as ethanol and n-heptane, and the mass ratio of the grinding aid to the reaction raw material (including vanadium pentoxide and network forming body oxide or precursor thereof) is (2-4): 1.
according to some embodiments of the application, during the mixing and ball milling in the first step, the ball milling speed is 200-400 rpm, the ball milling time is 1-3 h, and the mass ratio of the grinding balls to the materials is 15: 1.
according to some embodiments of the present application, in the first step, the drying temperature is 80-120 ℃ and the drying time is 1-3 hours.
According to some embodiments of the present application, the mixed material in the second step is melted in a crucible, and the crucible is a ceramic crucible or a platinum crucible.
According to some embodiments of the present application, in the second step, the temperature rise rate during melting is 5 to 10 ℃/min.
According to some embodiments of the present application, in step two, the quenching medium is ice water or liquid nitrogen.
According to some embodiments of the application, in the second step, the temperature rise rate during annealing is 1-10 ℃/min, the heat preservation time is 2-3 h, and the annealing is naturally cooled to the room temperature.
In a third aspect of the present application, there is provided an anode material comprising the anode active material described above, a binder, and a conductive agent
In a fourth aspect of the present application, a negative electrode sheet is provided, which includes a current collector and a negative electrode material layer on a surface of the current collector, wherein the negative electrode material layer includes the negative electrode material described above.
In a fifth aspect of the present application, a battery is provided, which includes the negative electrode sheet described above. The battery may further include a positive electrode sheet, an electrolyte, and a separator.
According to some embodiments of the present application, the battery is a lithium ion battery.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
The present application is further described with reference to the following figures and examples, in which:
fig. 1 is a binary phase diagram of a negative electrode active material according to an example of the present application.
Fig. 2 is an X-ray diffraction chart of the negative electrode active material of example 1 of the present application.
Fig. 3 is a graph showing cycle characteristics of a lithium ion battery produced by using the negative electrode active material of example 1 according to the present application.
Fig. 4 is a graph showing cycle characteristics of a lithium ion battery manufactured using the negative active material of comparative example 1 according to the present application.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, unless otherwise expressly limited, terms such as set, mounted, connected and the like should be construed broadly, and those skilled in the art can reasonably determine the specific meaning of the terms in the present application by combining the detailed contents of the technical solutions.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The present embodiment provides a negative electrode active material including amorphous vanadium pentoxide in which boron oxide is co-melted, and a molar ratio of vanadium to boron (or amorphous vanadium pentoxide to boron oxide) is 9: 1.
the preparation method of the negative active material comprises the following steps:
(1) 2.730g of vanadium pentoxide and 0.206g of boric acid were added to each ball mill pot, 10mL of anhydrous ethanol was added dropwise, and 44g of pellets were weighed into the ball mill pot. And fixing the ball milling tank on a ball mill, and performing ball milling for 1h at the ball milling rotation speed of 200rpm to uniformly mix the materials. And filtering the ball-milled materials, and drying in an oven at 80 ℃ for 1h to obtain a mixed material.
(2) 10g of the mixed material is put into a 30mL platinum crucible, then the crucible is put into a muffle furnace, the temperature is increased to 1000 ℃ at the heating rate of 5 ℃/min for melting, and after heat preservation is carried out for 2h, the mixed material is poured into ice water for quenching. Quenching, filtering, returning the filtered product to a muffle furnace for annealing, heating to 300 deg.C at a heating rate of 5 deg.C/min, maintaining for 2 hr, naturally cooling to room temperature, and grinding to obtain 9V2O5·1B2O3(the molar ratio of V to B is 9: 1, and the mass content of amorphous vanadium pentoxide is about 96%).
FIG. 1 is a graph of V prepared in the examples of the present application2O5·B2O3Binary phase diagram of glass negative active material. FIG. 2 is an X-ray diffraction pattern (XRD pattern) of the negative electrode active material, in which V is shown at the lowermost part2O5XRD data (PDF No.: 41-1426) of standard crystal cards, 9V of this example at the top2O5·1B2O3XRD data of the negative active material. As can be seen from the figure, the negative electrode active material provided in this example had an amorphous peak only within 20. ltoreq. 2. theta. ltoreq.30 without crystalThe common crystal diffraction peak of the bulk material shows that the amorphous negative active material is successfully prepared by the melting-quenching method.
Example 2
The embodiment provides a negative electrode active material, which includes amorphous vanadium pentoxide, in which boron oxide is co-melted, and a molar ratio of the amorphous vanadium pentoxide to the boron oxide is 8: 2.
the preparation method of the negative active material comprises the following steps:
(1) 3.640g of vanadium pentoxide and 0.618g of boric acid were added to each ball mill pot, 10mL of anhydrous ethanol was added dropwise, and 64g of pellets were weighed and placed in the ball mill pot. And fixing the ball milling tank on a ball mill, and performing ball milling for 1h at the ball milling rotation speed of 200rpm to uniformly mix the materials. And filtering the ball-milled materials, and drying in an oven at 80 ℃ for 1h to obtain a mixed material.
(2) 10g of the mixed material is put into a 30mL platinum crucible, then the crucible is put into a muffle furnace, the temperature is increased to 1000 ℃ at the heating rate of 5 ℃/min for melting, and after heat preservation is carried out for 2h, the mixed material is poured into ice water for quenching. Quenching, filtering, returning the filtered product to a muffle furnace for annealing, heating to 300 deg.C at a temperature rise rate of 5 deg.C/min, maintaining for 2 hr, naturally cooling to room temperature, and grinding to obtain 8V2O5·2B2O3(the molar ratio of V to B is 8: 2, and the mass content of amorphous vanadium pentoxide is about 91%).
Example 3
The present embodiment provides a negative electrode active material including amorphous vanadium pentoxide in which boron oxide is co-melted, and a molar ratio of vanadium to boron is 7: 3.
the preparation method of the negative active material comprises the following steps:
(1) 3.185g of vanadium pentoxide and 0.927g of boric acid are added into each ball milling pot, 10mL of absolute ethyl alcohol is added dropwise, and 62g of small balls are weighed and placed into the ball milling pot. And fixing the ball milling tank on a ball mill, and performing ball milling for 1h at the ball milling rotation speed of 200rpm to uniformly mix the materials. And filtering the ball-milled materials, and drying in an oven at 80 ℃ for 1h to obtain a mixed material.
(2) 10g of the mixed material is put into a 30mL platinum crucible and then put into a horseAnd (3) heating to 1000 ℃ at the heating rate of 5 ℃/min in a muffle furnace for melting, preserving heat for 2 hours, and pouring into ice water for quenching. Quenching, filtering, returning the filtered product to a muffle furnace for annealing, heating to 300 deg.C at a temperature rise rate of 5 deg.C/min, maintaining for 2 hr, naturally cooling to room temperature, and grinding to obtain 7V2O5·3B2O3(the molar ratio of V to B is 7: 3, and the mass content of amorphous vanadium pentoxide is about 86%).
Example 4
The present embodiment provides a negative electrode active material including amorphous vanadium pentoxide in which boron oxide is co-melted, and a molar ratio of vanadium to boron is 6: 4.
the preparation method of the negative active material comprises the following steps:
(1) 2.730g of vanadium pentoxide and 1.236g of boric acid are added into each ball milling tank, 10mL of absolute ethanol is added dropwise, and 60g of pellets are weighed and placed into the ball milling tank. And fixing the ball milling tank on a ball mill, and performing ball milling for 1h at the ball milling rotation speed of 200rpm to uniformly mix the materials. And filtering the ball-milled materials, and drying in an oven at 80 ℃ for 1h to obtain a mixed material.
(2) And putting 10g of the mixed material into a 30mL platinum crucible, then putting the crucible into a muffle furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min for melting, preserving heat for 2h, and pouring into ice water for quenching. Quenching, filtering, returning the filtered product to a muffle furnace for annealing, heating to 300 deg.C at a temperature rise rate of 5 deg.C/min, maintaining for 2 hr, naturally cooling to room temperature, and grinding to obtain 6V2O5·4B2O3(the molar ratio of V to B is 6: 4, and the mass content of amorphous vanadium pentoxide is about 80%).
Example 5
Electrochemical performance test
The negative electrode active materials of the embodiments 1 to 4 and the comparative example 1 are taken and sequentially prepared to obtain a negative electrode sheet and a lithium ion battery, and the first discharge specific capacity of the lithium ion battery under the normal temperature condition with the charge-discharge voltage of 0.01 to 3V and the current density of 100mA/g and the reversible specific capacity and the capacity retention rate after 500 charge-discharge cycles under the same condition are detected, and the results are shown in Table 1.
In the case of comparative example 1, which is a vanadium pentoxide crystal powder, the X-ray diffraction pattern thereof is seen in the middle of fig. 2, and as can be seen from the pattern, the XRD data of this substance is in agreement with that of a standard card, indicating that it is a vanadium pentoxide crystal.
The preparation method of the negative plate and the lithium ion battery comprises the following steps:
a negative electrode active material, conductive carbon black (conductive agent), polyvinylidene fluoride (binder) were prepared in a weight ratio of 8: 1: 1, dropwise adding N-methyl pyrrolidone (NMP), stirring for 12 hours on a magnetic stirrer, and mixing to obtain the cathode material. And uniformly coating the negative electrode material on a copper foil current collector, drying for 12 hours at 110 ℃ in a vacuum drying oven, and forming a negative electrode material layer on the surface of the copper foil current collector, thereby preparing the negative electrode sheet.
The prepared negative plate is used as a negative electrode, a commercial lithium plate is used as a counter electrode, a commercial Celgard 2300 is used as a diaphragm, and 1mol/L LiPF6The EC/DMC mixed solution (ethylene carbonate/dimethyl carbonate mixed solution, EC/DMC volume ratio is 3:7) is used as electrolyte to assemble CR2032 type button cell, and the lithium ion battery to be detected is obtained.
TABLE 1 results of electrochemical measurements
Fig. 3 is a cycle performance diagram of a lithium ion battery manufactured using the negative active material of example 1, fig. 4 is a cycle performance diagram of a lithium ion battery manufactured using the negative active material of comparative example 1, and it can be seen from the results of fig. 3 and 4 and table 1 that the first discharge specific capacity of a lithium battery manufactured using the negative active material including amorphous vanadium pentoxide can reach 676.4mAh/g, which is nearly doubled as compared to the existing crystalline graphite negative active material and exceeds the crystalline vanadium pentoxide in the comparative example by more than 10%; meanwhile, the capacity retention rate after 500 cycles is still maintained to be about 90 percent, and compared with the capacity reduction degree of the crystalline vanadium pentoxide in the comparative example, the capacity reduction degree is obviously lower, and the cycle stability is good.
The embodiments of the present application have been described in detail with reference to the drawings, but the present application is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
Claims (12)
1. An anode active material characterized by comprising amorphous vanadium pentoxide as an anode active material main body.
2. The negative electrode active material according to claim 1, wherein a network-forming oxide is co-fused with the amorphous vanadium pentoxide.
3. The negative electrode active material according to claim 2, wherein the network forming body oxide is at least one selected from the group consisting of boron oxide, silicon dioxide, phosphorus pentoxide, germanium dioxide, and tin dioxide.
4. The anode active material according to claim 2 or 3, wherein a molar ratio of the amorphous vanadium pentoxide to the network forming body oxide in the anode active material is not less than 3: 2.
5. the negative electrode active material according to any one of claims 1 to 3, wherein the negative electrode active material has an X-ray diffraction spectrum having an amorphous peak in a range of 20 ° ≦ 2 θ ≦ 30 °.
6. A method for producing a negative electrode active material, comprising the steps of:
the method comprises the following steps: uniformly mixing the oxide of the network forming body or the precursor thereof and vanadium pentoxide to obtain a mixed material;
step two: and melting the mixed material, quenching and annealing the molten product to obtain the negative active material.
7. The method according to claim 6, wherein the first step is specifically: and mixing and ball-milling the network forming body oxide or the precursor thereof, vanadium pentoxide and a grinding aid, and filtering and drying the ball-milled product to obtain a mixed material.
8. The preparation method according to claim 6, wherein in the second step, the melting temperature is 1000-1100 ℃, and the holding time is 1-2 h.
9. The method according to claim 6, wherein the annealing temperature in the second step is 300 to 350 ℃.
10. A negative electrode material characterized by comprising a binder, a conductive agent, and the negative electrode active material according to any one of claims 1 to 5.
11. A negative electrode sheet comprising a current collector and a negative electrode material layer on a surface of the current collector, wherein the negative electrode material layer comprises the negative electrode material according to claim 10.
12. A battery comprising the negative electrode sheet according to claim 11.
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| CN114300670A (en) * | 2021-12-28 | 2022-04-08 | 海南大学 | Vanadium-based glass negative electrode material, and preparation method and application thereof |
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