CN116314740B - Negative electrode active material, preparation method thereof, negative electrode plate, secondary battery and power utilization device - Google Patents

Negative electrode active material, preparation method thereof, negative electrode plate, secondary battery and power utilization device Download PDF

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CN116314740B
CN116314740B CN202310548002.3A CN202310548002A CN116314740B CN 116314740 B CN116314740 B CN 116314740B CN 202310548002 A CN202310548002 A CN 202310548002A CN 116314740 B CN116314740 B CN 116314740B
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active material
negative electrode
electrode active
niobium
material according
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CN116314740A (en
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张俊英
赵黎江
刘星华
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Beihang University
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Beihang University
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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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application relates to a negative electrode active material, a preparation method thereof, a negative electrode plate, a secondary battery and an electric device. The negative electrode active material comprises a chemical composition of Nb 18 P 2.5 O 50 Niobium-based oxide of (b). Nb (Nb) 18 P 2.5 O 50 Is of a non-stoichiometric ratioThe oxide has better electronic conductivity and ionic conductivity. The negative electrode active material has higher lithium ion transmission rate and better multiplying power performance. In addition, the negative electrode active material also has good cycle stability.

Description

Negative electrode active material, preparation method thereof, negative electrode plate, secondary battery and power utilization device
Technical Field
The application relates to the technical field of secondary batteries, in particular to a negative electrode active material and a preparation method thereof, a negative electrode plate, a secondary battery and an electric device.
Background
The lithium ion battery has the characteristics of high energy density, high average output voltage, small self-discharge, no memory effect and the like, and is widely applied to the fields of electric automobiles, large-scale energy storage equipment and the like. The low charging efficiency is one of the main problems restricting the rapid development of new energy automobiles, and shortening the charging time of the power battery has important significance in relieving urban traffic problems and optimizing a power grid.
The niobium-based oxide is a novel lithium ion battery cathode material, and is widely focused in the field of quick-charging batteries due to the advantages of quick ion diffusion, stable structure and the like. However, conventional niobium-based oxides have poor conductivity, and the rate of charge and discharge is increased, which results in a significant decrease in the rate characteristics. And the fast charge rate (fast ion/electron transport) of conventional niobium-based oxides still is difficult to meet the needs of the application.
Disclosure of Invention
Based on the above, it is necessary to provide a negative electrode active material having a high lithium ion transmission rate and good rate capability, and a method for preparing the same.
In addition, a negative electrode plate, a secondary battery and an electric device containing the negative electrode active material are also provided.
In one aspect of the present application, there is provided a negative electrode active material comprising a chemical composition of Nb 18 P 2.5 O 50 Niobium-based oxide of (b).
In some embodiments, the niobium-based oxide has a particle size of 1 μm to 10 μm.
In some of these embodiments, the niobium-based oxide has an orthorhombic ReO 3 Structure is as follows.
In some embodiments, the negative electrode active material has an electron conductivity of 3 x 10 -5 S m -1 ~5*10 -5 S m -1 。
In some of these embodiments, the negative electrode active material has an ionic conductivity of 10 -8 cm 2 S -1 ~10 -7 cm 2 S -1 。
In a second aspect, the present application also provides a method for preparing the above negative electrode active material, including the steps of:
mixing, grinding and drying a niobium source and a phosphorus source to prepare a mixture;
sintering the mixture under an air atmosphere to prepare the niobium-based oxide.
In some of these embodiments, the niobium source comprises niobium oxide; the phosphorus source comprises at least one of monoammonium phosphate and red phosphorus.
In some embodiments, the step of sintering satisfies at least one condition of (1) - (3):
(1) The sintering temperature is 1000-1200 ℃;
(2) The sintering time is 15-80 hours;
(3) In the sintering step, the temperature is raised to the sintering temperature at a heating rate of 0.5-1 ℃/min.
In some embodiments, the milling is performed by ball milling; the rotational speed of the ball milling is 300 rpm-400 rpm, and the time of the ball milling is 5 h-8 h.
In a third aspect, the present application also provides a negative electrode tab, including the negative electrode active material described above or a negative electrode active material prepared according to the preparation method of the negative electrode active material described above.
In a fourth aspect, the application also provides a secondary battery, which comprises the negative electrode plate.
In a fifth aspect, the present application also provides an electric device, including the above secondary battery.
The anode active material provided by the embodiment of the application comprises a chemical composition of Nb 18 P 2.5 O 50 Niobium-based oxide of (b). Nb (Nb) 18 P 2.5 O 50 Is of a non-stoichiometric ratioThe oxide has better electronic conductivity and ionic conductivity. The negative electrode active material has higher lithium ion transmission rate and better rate capability.
In addition, the negative electrode active material has good cycle stability.
Drawings
FIG. 1 is an X-ray diffraction pattern and a theoretical simulation calculation of a valence band spectrum of a negative electrode active material of example 1 of the present application;
FIG. 2 is a scanning electron micrograph of a negative electrode active material of example 1 of the present application, wherein the scale is 200nm;
FIG. 3 is a scanning electron micrograph of a negative electrode active material of example 1 of the present application, wherein the scale is 2. Mu.m;
fig. 4 is an electrochemical curve of the anode active material of example 1 of the present application;
fig. 5 is a graph showing the lithium ion diffusion coefficient of the anode active material of example 1 of the present application;
fig. 6 is a CV curve of the anode active material of example 1 of the present application;
fig. 7 is a view showing the rate performance of the anode active material of example 1 of the present application;
fig. 8 is a cycle performance chart of the anode active material of example 1 of the present application;
fig. 9 is a cycle performance chart of the anode active material of example 2 of the present application;
fig. 10 is a cycle performance chart of the anode active material of example 3 of the present application;
FIG. 11 is an X-ray diffraction pattern and a theoretical simulation calculated valence band spectrum of the negative electrode active material of comparative example 1 of the present application;
fig. 12 is a scanning electron micrograph of a negative electrode active material of comparative example 1 of the present application, in which the scale is 1 μm.
Detailed Description
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to the appended drawings. Preferred embodiments of the present application are shown in the drawings. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
In this context, the technical features described in open form include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.
In this context, reference to a numerical interval is to be construed as continuous and includes the minimum and maximum values of the range, and each value between such minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
In this context, referring to units of data range, if a unit is only carried after the right endpoint, the units representing the left and right endpoints are identical. For example, 800-850 nm indicates that the units of the left end point "800" and the right end point "850" are nm (nanometers).
Only a few numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
The temperature parameter herein is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The terms "first," "second," and the like herein are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present application, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
An embodiment of the present application provides a negative electrode active material comprising a chemical composition of Nb 18 P 2.5 O 50 Niobium-based oxide of (b).
Nb 18 P 2.5 O 50 Is of a non-stoichiometric ratioThe increase in the ratio of the oxide to the phosphorus in the tetrahedra results in a decrease in the oxidation state of niobium and a partial filling of the 4d orbitals, which in turn exhibits an increase in conductivity. In addition, nb 18 P 2.5 O 50 And the lithium ion diffusion coefficient in the crystal is superior to that of other niobium-based materials, and the crystal has excellent electron conductivity and ion conductivity. The negative electrode active material has higher lithium ion transmission rate and better rate capability. In addition, the negative electrode active material has good cycle stability.
In some of these embodiments, the niobium-based oxide has a particle size of 1 μm to 10 μm. The particle size of the niobium-based oxide is in the range, and the negative electrode plate prepared by using the negative electrode active material has higher compaction density and structural stability. Alternatively, the particle size of the niobium-based oxide is in the range of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or any number above. Further, the particle size of the niobium-based oxide is 2 μm to 5 μm.
In some of these embodiments, the niobium-based oxide has an orthogonal phase ReO 3 Structure is as follows.
In some of these embodiments, the electron conductivity of the anode active material is 3×10 -5 S m -1 ~5*10 -5 S m -1 . The electron conductivity of the anode active material is in the range, and the anode active material has better conductivity, is favorable for transmitting electrons to a current collector, and improves the quick charge performance of the lithium ion battery.
In some of these embodiments, the negative electrode active material has an ionic conductivity of 10 -8 cm 2 S -1 ~10 -7 cm 2 S -1 . The ion conductivity of the anode active material is in the range, and the anode active material has better lithium ion transmission performance, is favorable for rapid deintercalation of lithium ions, and improves the rapid charging performance of a lithium ion battery.
In a second aspect, the present application also provides a method for preparing the above-mentioned anode active material, which includes the following steps S110 and S120 to prepare a niobium-based oxide.
Step S110: mixing, grinding and drying a niobium source and a phosphorus source to prepare a mixture.
In some of these embodiments, the niobium source comprises niobium oxide.
In some embodiments, the niobium oxide has a particle size of 50nm to 200 nm. Optionally, the niobium oxide has a particle size in the range of 50nm, 80 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200nm, or any number of values above.
In some of these embodiments, the phosphorus source comprises at least one of monoammonium phosphate and red phosphorus.
In some of these embodiments, the milling is performed by ball milling.
In some embodiments, the rotational speed of the ball mill is 300 rpm to 400 rpm, and the time of the ball mill is 5 hours to 8 hours. Alternatively, the rotational speed of the ball mill is 300 rpm, 350 rpm, 400 rpm, or any combination thereof. Alternatively, the ball milling time is in the range of 5 h, 6 h, 7 h, 8 h or any number of values above.
Step S120: the mixture was sintered under an air atmosphere to prepare a niobium-based oxide.
In some embodiments, in step S120, the sintering temperature is 1000 ℃ to 1200 ℃. Alternatively, the sintering temperature is in the range of 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or any number above.
In some embodiments, in step S120, the sintering time is 15 h to 80 h. Optionally, the sintering is performed for a time period within the range of 15 h, 16 h, 18 h, 20 h, 24 h, 30 h, 36 h, 40 h, 48 h, 60 h, 70 h, 80 h, or any number thereof.
In some embodiments, in step S120, the temperature is raised to the sintering temperature at a temperature-raising rate of 0.5 ℃/min to 1 ℃/min. Optionally, the heating rate is in the range of 0.5 ℃/min, 0.6 ℃/min, 0.7 ℃/min, 0.8 ℃/min, 0.9 ℃/min, 1 ℃/min, or any value combination thereof.
According to the preparation method of the negative electrode active material, the niobium source and the phosphorus source are mixed and ball-milled, then sintered, and the niobium-based oxide is prepared through a high-temperature solid phase method, so that the prepared niobium-based oxide has a proper particle size, and the negative electrode active material has a good lithium ion transmission performance and a good multiplying power performance. In addition, the preparation method has the advantages of simple equipment, simple and convenient operation and lower process cost.
In a third aspect, the present application also provides a negative electrode tab, including the negative electrode active material described above or a negative electrode active material prepared according to the preparation method of the negative electrode active material described above.
In some of these embodiments, the negative electrode tab includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer including the negative electrode active material described above.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode active material layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some of these embodiments, the negative current collector may be a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some of these embodiments, the anode active material layer may further optionally include a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some of these embodiments, the negative electrode active material layer may further optionally include a binder. The binder may be at least one selected from polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), polytetrafluoroethylene emulsion (PTFE), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), and Polyacrylamide (PAM).
In a fourth aspect, the application also provides a secondary battery, which comprises the negative electrode plate.
In some of these embodiments, the secondary battery includes, but is not limited to, one of a lithium ion battery and a sodium ion battery.
In some of these embodiments, the secondary battery further includes a positive electrode tab, a separator, and an electrolyte. In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
In a fifth aspect, the present application also provides an electric device, including the above secondary battery.
In some of these embodiments, the powered device may include, but is not limited to, a mobile device (e.g., a cell phone, a notebook computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a watercraft, a satellite, an energy storage system, etc.
In order to make the objects, technical solutions and advantages of the present application more concise, the present application will be described in the following specific examples, but the present application is by no means limited to these examples. The following examples are only preferred embodiments of the present application, which can be used to describe the present application, and should not be construed as limiting the scope of the application. It should be noted that any modifications, equivalent substitutions and improvements made within the spirit and principle of the present application should be included in the protection scope of the present application.
In order to better illustrate the present application, the following description of the present application will be given with reference to examples. The following are specific examples.
Example 1
The preparation method of the anode active material of the present embodiment includes the steps of: 0.0052 mol of niobium oxide (T phase, 50-200 nm) and 0.001 mol of ammonium dihydrogen phosphate were weighed and dispersed in 50mL absolute ethanol, and stirred for 720 minutes, to obtain a slurry. The slurry is manually ground for 1 hour and then transferred into blast drying for heating and drying. And transferring the dried powder into a covered alumina crucible, heating to 1100 ℃ at a heating rate of 0.5 ℃/min, maintaining for 20 hours, and naturally cooling to obtain the anode active material.
Referring to fig. 1, an X-ray diffraction pattern and a valence band spectrum calculated by theoretical simulation of the anode active material of the present embodiment are shown. According to the X-ray diffraction pattern and the element analysis result (P: nb=1.22:9at%), the negative electrode active material of this example had a chemical composition of Nb 18 P 2.5 O 50 . Referring to fig. 2 and 3, scanning electron microscope images of the negative electrode active material of the present embodiment are shown, and the particle size of the negative electrode active material of the present embodiment is 2 μm to 5 μm.
Example 2
The preparation method of the anode active material of the present embodiment includes the steps of: 0.0052 mol of niobium oxide (T phase, 50-200 nm) and 0.001 mol of red phosphorus are weighed and dispersed into 50ml absolute ethyl alcohol to be stirred for 720 min, and slurry is obtained. The slurry is manually ground for 1 hour and then transferred into blast drying for heating and drying. And transferring the dried powder into a covered alumina crucible, heating to 1100 ℃ at a heating rate of 0.5 ℃/min, maintaining for 20 hours, and naturally cooling to obtain the anode active material.
According to the X-ray diffraction pattern and the elemental analysis (P: nb=1.20:9at%) results, the negative electrode active material of the present example had a chemical composition of Nb 18 P 2.5 O 50 . The particle diameter of the negative electrode active material of this example was 2 μm to 5 μm as observed by a scanning electron microscope.
Example 3
The preparation method of the anode active material of the present embodiment includes the steps of: 0.0052 mol of niobium oxide (T phase, 50-200 nm) and 0.001 mol of ammonium dihydrogen phosphate were weighed and dispersed in 50ml of absolute ethanol, and stirred for 30 min. Then transferring the slurry into a ball mill to rotate at 300 rpm, ball milling 6 h, and transferring the slurry into blast drying for heating and drying. And transferring the dried powder into a covered alumina crucible, heating to 1200 ℃ at a heating rate of 0.5 ℃/min, maintaining for 20 hours, and naturally cooling to obtain the anode active material.
According to the X-ray diffraction pattern and the element analysis result (P: nb=1.19:9at%), the negative electrode active material of this example had a chemical composition of Nb 18 P 2.5 O 50 . The particle diameter of the negative electrode active material of this example was 2 μm to 5 μm as observed by a scanning electron microscope.
Comparative example 1
The negative electrode active material of the embodiment has a chemical composition of Nb 18 P 2 O 50 The element analysis result shows that the P is Nb=0.93:9at%, and the particle size of the anode active material is 2-5 μm.
Preparing a negative electrode plate:
mixing and dispersing the anode active materials of examples 1-3 or comparative example 1, acetylene black serving as a conductive agent and SBR serving as a binder in deionized water according to a mass ratio of 80:10:10 to prepare anode slurry; and coating the negative electrode slurry on a copper foil, drying and cold pressing to obtain a negative electrode plate.
Half cell preparation:
and a lithium metal counter electrode and a glass fiber isolating film are adopted. Preparing a bare cell by laminating a lithium metal counter electrode, an isolating membrane and a negative electrode plate, packaging the bare cell in a CR2032 shell, and injecting electrolyte, wherein the electrolyte comprises 1mol of LiPF 6 Dissolved in ec:dmc:emc=1:1:1 (volume ratio), half cells were prepared.
Test part:
electron conductivity test: the electronic conductivity is obtained by adopting a direct current method and a direct probe measurement method.
Ion conductivity (lithium ion diffusion coefficient) test: the ion conductivity was obtained using the electrochemical galvanometric titration technique (GITT) test. 100mA g was used -1 The current density is charged/discharged for 5 circles by 100mA g -1 Titration was performed at current density for 10 minutes and relaxation time for 8 hours, and the above procedure was repeated until the cut-off voltage was close to 1V.
And (3) multiplying power performance test: 100, 200, 500, 1000, 2000, 4000, 6000 8000, 10000, 12000, 14000, 16000, 18000, 20000 mA g respectively -1 The charge/discharge test was repeated for 2 cycles at a current density of 1-2.5V.
Cycle stability test: at 100mA g -1 The charge/discharge test was repeated 5 times at current density, and then 4000 mA g was used -1 Is tested 1000 times.
Performance data of the negative electrode active materials and lithium ion batteries prepared in examples 1 to 3 and comparative example 1 are recorded in table 1.
TABLE 1
Referring to fig. 4 to 6, the electrochemical performance and the lithium ion diffusion coefficient of the anode active material of example 1 are shown. As can be seen from the figure, the anode active material of example 1 has a high lithium ion diffusion coefficient. Referring to FIG. 7, it is a real objectA rate performance test chart of the anode active material of example 1; as can be seen from the figure, the anode active material of example 1 was at 0.1A g -1 Gram capacity of charge-discharge cycle under current is 225 mAh g -1 At 20A g -1 The gram capacity of charge-discharge cycle under current is 125 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the It can be seen that the anode active material of example 1 still has a high capacity retention during high-rate charge and discharge. Referring to FIGS. 8 to 10, the negative electrode active materials of examples 1 to 3 were prepared at 4000 mA g -1 As can be seen from the graph, the negative electrode active materials of examples 1 to 3 showed a change in gram-volume of charge-discharge cycles at 4000 mA g -1 The capacity retention rate is higher after 600-1000 charge-discharge cycles under current, and the cycle stability of the anode active material is better.
As can be seen from the data in Table 1, the negative electrode active materials of examples 1 to 3 have both higher electron conductivity and ion conductivity than the negative electrode active material of comparative example 1, and the negative electrode active material has a high rate (10 Ag -1 ) The capacity retention rate of the lower charge and discharge is high.
Referring to table 2, specific capacities of the negative electrode active materials of examples 1 to 3 and comparative example 1 at different current densities are shown.
TABLE 2
As can be seen from the data relating to Table 2, the negative electrode active materials of examples 1 to 3 were prepared at 100mA g -1 The specific capacity at 4000 mA g was equivalent to that of the negative electrode active material of comparative example 1 -1 、8000 mA g -1 The specific capacity is higher, and it can be seen that the capacity retention rate of examples 1-3 at high magnification is higher, and the rate performance is better.
Referring to Table 3, the anode active materials of examples 1 to 3 and comparative example 1 were each at 4000 mA g -1 、8000 mA g -1 Capacity retention after 1000 charge and discharge cycles.
TABLE 3 Table 3
As can be seen from the data related to table 3, the negative electrode active materials of examples 1 to 3 have better cycle stability than comparative example 1. At 4000 mA g -1 The capacity retention rate of the circulating ring after 1000 times is 87% -95%; at 8000 mA g -1 After 1000 times of circulation, the capacity retention rate is 68% -78%.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art obtain technical solutions through logical analysis, reasoning or limited experiments, all of which are within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.

Claims (11)

1. A negative electrode active material comprising a composition of Nb 18 P 2.5 O 50 The particle size of the niobium-based oxide is 1-10 mu m;
the preparation method of the anode active material comprises the following steps of:
mixing and grinding a niobium source and a phosphorus source, and drying to prepare a mixture, wherein the grinding mode is ball milling;
sintering the mixture under an air atmosphere to prepare the niobium-based oxide.
2. The anode active material according to claim 1, wherein the particle diameter of the niobium-based oxide is 2 μm to 5 μm.
3. The anode active material according to claim 1, wherein the niobium-based oxide has an orthorhombic ReO 3 Structure is as follows.
4. The anode active material according to claim 1, wherein the anode active material has an electron conductivity of 3 x 10 -5 S m -1 ~5×10 -5 S m -1 。
5. The method for producing a negative electrode active material according to any one of claims 1 to 4, comprising the steps of:
mixing and grinding a niobium source and a phosphorus source, and drying to prepare a mixture, wherein the grinding mode is ball milling;
sintering the mixture under an air atmosphere to prepare the niobium-based oxide.
6. The method for producing a negative electrode active material according to claim 5, wherein the niobium source comprises niobium oxide; the phosphorus source comprises at least one of monoammonium phosphate and red phosphorus.
7. The method for producing a negative electrode active material according to claim 5, wherein the step of sintering satisfies at least one of the conditions (1) to (3):
(1) The sintering temperature is 1000-1200 ℃;
(2) The sintering time is 15-80 hours;
(3) In the sintering step, the temperature is raised to the sintering temperature at a heating rate of 0.5-1 ℃/min.
8. The method for preparing a negative electrode active material according to any one of claims 5 to 7, wherein the rotational speed of the ball mill is 300 rpm to 400 rpm, and the time of the ball mill is 5 hours to 8 hours.
9. A negative electrode sheet, characterized by comprising the negative electrode active material according to any one of claims 1 to 4 or the negative electrode active material produced by the method for producing a negative electrode active material according to any one of claims 5 to 8.
10. A secondary battery comprising the negative electrode tab of claim 9.
11. An electric device comprising the secondary battery according to claim 10.
CN202310548002.3A 2023-05-16 2023-05-16 Negative electrode active material, preparation method thereof, negative electrode plate, secondary battery and power utilization device Active CN116314740B (en)

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