CN113540397A - Lithium titanate battery pole piece and preparation method and application thereof - Google Patents
Lithium titanate battery pole piece and preparation method and application thereof Download PDFInfo
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- CN113540397A CN113540397A CN202110621387.2A CN202110621387A CN113540397A CN 113540397 A CN113540397 A CN 113540397A CN 202110621387 A CN202110621387 A CN 202110621387A CN 113540397 A CN113540397 A CN 113540397A
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- lithium titanate
- conductive agent
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- titanate battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 115
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000006258 conductive agent Substances 0.000 claims abstract description 74
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- 238000000034 method Methods 0.000 claims abstract description 20
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- 238000004544 sputter deposition Methods 0.000 claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/088—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or Pb and B representing a refractory or rare earth metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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 relates to a lithium titanate battery pole piece and a preparation method and application thereof. The lithium titanate battery pole piece comprises a current collector, an active material layer and a conductive agent layer which are sequentially stacked. The conductive agent layer is arranged on the surface of the active material layer, so that the active material lithium titanate in the active material layer can be effectively protected and isolated from moisture, the stability of the lithium titanate battery pole piece is ensured, and the lithium titanate battery pole piece is good in stability and long-acting cycle performance. The preparation method of the lithium titanate battery pole piece adopts a magnetron sputtering process, particles of the composite target material can be deposited on the surface of the current collector to form an active material layer and a conductive agent layer under the action of a magnetic field, and components such as a binder, a dispersing agent and the like are not required to be added in the preparation process, so that the introduction of moisture in the preparation process is avoided, and the defect caused by the reaction of active material lithium titanate and water is avoided.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium titanate battery pole piece and a preparation method and application thereof.
Background
Lithium ion batteries are a type of battery that uses a material containing lithium as an electrode and relies on lithium ions to move between a positive electrode and a negative electrode to operate. Lithium ion batteries are a class of lithium batteries that have many advantages such as high energy density, high power density, and long cycle life, and thus have drawn great attention in the fields of portable electronic devices, power batteries, energy storage batteries, and the like.
Lithium titanate (Li)4Ti5O12) Because of its good stability, it is widely used in lithium ion battery cathode material. However, lithium titanate negative electrode materials are very likely to react with trace amounts of moisture inside the lithium ion battery, resulting in the generation of gases having hydrogen, carbon monoxide, carbon dioxide, and the like as main components after charge and discharge cycles of the lithium ion battery, thereby causing the lithium ion battery to bulge. The generation of these gases can lead to an increase in the internal pressure of the battery, affecting the long-term stability and safety of the lithium ion battery. However, due to the limitation of the manufacturing process, trace moisture inside the lithium ion battery is generally difficult to remove, and moisture in the order of several hundred ppm exists in the positive electrode, the negative electrode sheet, and the electrolyte. In addition, the organic dispersant N-methyl pyrrolidone (NMP) used in the traditional pole piece coating process also contains a certain amount of moisture, and the raw materials all provide challenges for long-acting stable work of lithium ion batteries based on lithium titanate cathodes.
Disclosure of Invention
Therefore, a lithium titanate battery pole piece with high stability of active materials and good cycle performance, and a preparation method and application thereof are needed to be provided.
In one aspect of the present invention, a lithium titanate battery electrode plate is provided, which includes:
a current collector;
an active layer including an active material and a conductive agent; the active material is lithium titanate; the active layer is disposed on at least one surface of the current collector; and
and the conductive agent layer is arranged on the surface of the active layer and covers the active layer.
In some of these embodiments, the current collector is selected from one of a metallic material and a flexible carbon-based material.
In some of these embodiments, the flexible carbon-based material is selected from at least one of a carbon nanotube film, a conductive carbon cloth, a conductive carbon paper, and a graphene foam.
In some of these embodiments, the conductive agent in the active layer and the conductive agent layer are each independently selected from at least one of graphite, conductive carbon black, acetylene black, carbon nanotubes, and graphene.
In some embodiments, the active material lithium titanate and the conductive agent in the active layer are in a mass ratio of (90-100): (0-10).
In some embodiments, the mass ratio of the active agent layer to the conductive agent layer is (90-100): (1-10).
The invention also provides a preparation method of the lithium titanate battery pole piece, which comprises the following steps:
sequentially forming a laminated active material layer and a conductive agent layer on the surface of a current collector by adopting a magnetron sputtering process; wherein the active layer includes an active material and a first conductive agent; the active material is lithium titanate; the conductive agent layer includes a second conductive agent.
In some embodiments, the step of sequentially forming the stacked active layer and the conductive agent layer on the surface of the current collector by using a magnetron sputtering process includes:
grinding and mixing the active material and the first conductive agent to obtain mixed powder;
sequentially adding the second conductive agent and the mixed powder into a die, and performing dry pressing to obtain a composite target material;
and putting the clean current collector into a magnetron sputtering instrument, and performing magnetron sputtering by taking the composite target material as a sputtering material so that the composite target material sequentially forms an active material layer and a conductive agent layer on the current collector.
On the other hand, the invention also provides the application of the lithium titanate battery pole piece or the lithium titanate battery pole piece obtained by the preparation method of the lithium titanate battery pole piece in the preparation of the lithium ion battery.
On the other hand, the invention also provides a lithium ion battery, wherein the negative electrode plate of the lithium ion battery adopts the lithium titanate battery electrode plate or the lithium titanate battery electrode plate obtained by the preparation method of the lithium titanate battery electrode plate.
The lithium titanate battery pole piece comprises a current collector, an active material layer and a conductive agent layer. The active layer comprises an active material and a conductive agent, and the conductive agent layer covers the surface of the active layer. The conductive agent layer is arranged on the surface of the active layer, so that lithium titanate in the active layer can be effectively protected and isolated from moisture, the stability of the lithium titanate battery pole piece is ensured, and the lithium titanate battery pole piece is good in stability and long-acting cycle performance.
The preparation method of the lithium titanate battery pole piece is based on a magnetron sputtering process, the lithium titanate, the first conductive agent and the second conductive agent are prepared into the composite target material, the current collector is used as a substrate, the composite target material is used as a sputtering material, and the surface of the current collector is covered with the active material layer and the conductive layer. Compared with the traditional coating process for preparing the battery pole piece, the preparation method of the lithium titanate battery pole piece adopts the magnetron sputtering process, the particles of the composite target material can be deposited on the surface of the current collector under the action of a magnetic field, and the components such as a binder, a dispersing agent and the like are not required to be added in the preparation process, so that the introduction of moisture in the preparation process is avoided, and the defects caused by the reaction of the active material lithium titanate and water are avoided. In addition, the lithium titanate battery pole piece obtained by the preparation method has the advantages that the binding force between the active layer and the current collector and the binding force between the conductive agent layer and the current collector are strong, the uniformity of particles of the active layer is good, the agglomeration is not easy, and the stability of the lithium titanate battery pole piece is high. And the thicknesses of the active material layer and the conductive agent layer can be adjusted by controlling the magnetron sputtering time. The active material layer does not need to be added with components such as a binder, a dispersing agent and the like, and the active material has high occupation ratio, so that the active material layer has high energy density.
Drawings
Fig. 1 is a schematic structural diagram of a lithium titanate battery electrode sheet 10 according to an embodiment of the present invention; a current collector 100, an active layer 200, a conductive agent layer 300;
fig. 2 is a flow chart of a method for preparing a lithium titanate battery pole piece according to an embodiment of the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention 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 the description of the present invention, it is to be understood that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a lithium titanate battery pole piece 10, including: a current collector 100, an active layer 200, and a conductive agent layer 300.
The active layer 200 includes an active material and a conductive agent; the active material is lithium titanate; the active layer 200 is disposed on at least one surface of the current collector 100. It is understood that in some embodiments, the active layer 200 may be disposed on both opposing surfaces of the current collector 100; still alternatively, the active layer 200 completely covers the outer surface of the current collector 100.
The conductive agent layer 300 is disposed on the surface of the active layer 200 and covers the active layer 200.
The lithium titanate battery pole piece 10 includes a current collector 100, an active material layer 200, and a conductive agent layer 300. The active layer 200 includes an active material lithium titanate and a conductive agent, and the conductive agent layer 300 covers the surface of the active layer. The conductive agent layer 300 is arranged on the surface of the active material layer 200, so that the active material lithium titanate in the active material layer can be effectively protected and isolated from moisture, the stability of the lithium titanate battery pole piece is guaranteed, and the lithium titanate battery pole piece is good in stability and long-acting cycle performance.
In some of these embodiments, the current collector 100 may be selected from one of a metal material and a flexible carbon-based material.
In some of these embodiments, the current collector 100 may be selected from at least one of copper foil, aluminum foil, and copper foam.
The flexible carbon-based material has flexibility and conductivity, and the flexible lithium titanate battery pole piece can be obtained by using the flexible carbon-based material as the current collector 100, and the battery pole piece has good bending performance. In some of these embodiments, the flexible carbon-based material is selected from at least one of a carbon nanotube film, a conductive carbon cloth, a conductive carbon paper, and a graphene foam.
In some of these embodiments, the conductive agent in the active layer 200 and the conductive agent layer 300 are each independently selected from at least one of graphite, conductive carbon black, acetylene black, carbon nanotubes, and graphene. In some embodiments, the conductive agent in the active layer 200 and the conductive agent layer 300 is graphite.
In some embodiments, in the active material layer 200, the mass ratio of the active material to the conductive agent is (90-100): (0-10). It can be understood that a certain amount of conductive agent is added into the active material layer 200, so that the conductivity of the battery pole piece can be improved, and the rate capability of the material can be improved. On the other hand, the conductive agent can coat lithium titanate, so that the contact between the lithium titanate and water is reduced, and the gas generated by the contact reaction between the lithium titanate and the water is avoided.
In some embodiments, the mass ratio of the active material layer 200 to the conductive agent layer 300 is (90-100): (1-10).
In some embodiments, the mass ratio of the active layer 200 to the conductive agent layer 300 is 100: 10.
the invention also provides a preparation method of the lithium titanate battery pole piece, which comprises the following steps:
sequentially forming a laminated active material layer and a conductive agent layer on the surface of a current collector by adopting a magnetron sputtering process; wherein the active layer comprises an active material and a first conductive agent; the active material is lithium titanate; the conductive agent layer includes a second conductive agent.
Magnetron sputtering is one type of Physical Vapor Deposition (PVD). The general sputtering method can be used for preparing multi-materials such as metal, semiconductor, insulator and the like, and has the advantages of simple equipment, easy control, large film coating area, strong adhesive force and the like. Magnetron sputtering is a process in which incident particles collide with a target material so that the particles on the surface of the target material are sputtered and deposited on a substrate.
The preparation method of the lithium titanate battery pole piece is based on a magnetron sputtering process, the active material lithium titanate, the first conductive agent and the second conductive agent are prepared into the composite target material, the current collector is used as a substrate, the composite target material is used as a sputtering material, and the surface of the current collector is covered with the active material layer and the conductive layer. Compared with the traditional coating process for preparing the battery pole piece, the preparation method of the lithium titanate battery pole piece adopts the magnetron sputtering process, the particles of the composite target material can be deposited on the surface of the current collector under the action of a magnetic field, and the components such as a binder, a dispersing agent and the like are not required to be added in the preparation process, so that the introduction of moisture in the preparation process is avoided, and the defects caused by the reaction of the active material lithium titanate and water are avoided.
In addition, the lithium titanate battery pole piece obtained by the preparation method has the advantages that the binding force between the active material layer and the current collector is strong, the uniformity and the dispersibility of active particles of the active material layer are good, the active particles are not easy to agglomerate, the stability of the lithium titanate battery pole piece is high, and particularly when the lithium titanate battery pole piece is applied to the preparation of a flexible electrode plate, the binding strength between the active material layer and the current collector can be improved, and the bending performance of the pole piece can be improved. And the thicknesses of the active material layer and the conductive agent layer can be accurately regulated and controlled by controlling the magnetron sputtering time. The active material layer does not need to be added with components such as a binder, a dispersing agent and the like, and the occupation ratio of the active material is high, so that the active material layer has high energy density.
Referring to fig. 2, in some embodiments, the step of sequentially forming the stacked active material layer and the conductive agent layer on the surface of the current collector by using a magnetron sputtering process includes steps S1 to S3.
Step S1: grinding and mixing the active material and the first conductive agent to obtain mixed powder;
step S2: sequentially adding a second conductive agent and the mixed powder into a die, and performing dry pressing to obtain a composite target material;
step S3: and (3) placing the clean current collector in a magnetron sputtering instrument, and performing magnetron sputtering by taking the composite target as a sputtering material so that the composite target forms an active material layer and a conductive agent layer on the current collector in sequence.
In some of these embodiments, the first conductive agent and the second conductive agent are each independently selected from at least one of graphite, conductive carbon black, acetylene black, carbon nanotubes, and graphene.
In some of these embodiments, the magnetron sputtering is performed under an inert gas atmosphere. In some embodiments, the inert gas is high purity argon.
In some embodiments, before step S3, the method further includes the following steps:
placing the current collector in absolute ethyl alcohol or acetone for ultrasonic cleaning;
and drying the cleaned current collector.
In some of the embodiments, the time for ultrasonic cleaning is 5 to 15 minutes.
In some of these embodiments, the drying step is performed in a vacuum oven; the drying temperature is 80-85 ℃; the drying time is 30-45 minutes.
In some of these embodiments, the milling step in step S1 is performed in a ball mill.
In some embodiments, step S1 specifically includes: adding an active material lithium titanate and a first conductive agent into a ball milling tank, and adding absolute ethyl alcohol into the ball milling tank until the active material lithium titanate, the first conductive agent and grinding balls just submerge. The ball mill jar was mounted on a ball mill and run at 300rpm for 10 hours. The mixed powder is taken out and dried for 5 hours in vacuum at 120 ℃.
In some embodiments, in step S2, the copper disc is used as a mold, the second conductive agent is spread in the copper disc, then the mixed powder is spread on the surface of the second conductive agent, and the composite target is obtained by dry pressing. In some embodiments, the dry-pressing is a one-way dry press at a pressure of 6 tons.
In some of these embodiments, step S3 includes:
putting the current collector and the composite target material into a magnetron sputtering instrument, and vacuumizing a sputtering cavity to 5.0 multiplied by 10-4Pa；
Heating to a preset temperature at a heating rate of 30 ℃/min;
introducing inert gas as sputtering gas, wherein the pressure in the cavity is 0.1-0.5 Pa;
pre-sputtering for 10-30 minutes to clean impurities such as an oxide layer on the surface of the target material;
carrying out magnetron sputtering according to preset parameters.
In some embodiments, the magnetron sputtering power is 200W-600W, the distance between the target and the current collector is 5-10 cm, and the magnetron sputtering time is 1-8 hours. The thicknesses of the active layer and the conductive agent layer can be controlled by controlling the magnetron sputtering time.
In some embodiments, the temperature of the current collector is 350-550 ℃; the current collector rotates at the rotating speed of 10r/min in the magnetron sputtering process.
In some embodiments, after sputtering is finished, the lithium titanate battery pole piece is naturally cooled, inert gas is kept introduced before the temperature is reduced to 100 ℃, the gas is closed after the temperature is reduced to 100 ℃, and the lithium titanate battery pole piece is taken out after the temperature is reduced to room temperature.
The invention further provides an application of the lithium titanate battery pole piece or the lithium titanate battery pole piece obtained by the preparation method of the lithium titanate battery pole piece in the preparation of a lithium ion battery.
The invention further provides a lithium ion battery, wherein the negative electrode plate of the lithium ion battery adopts the lithium titanate battery electrode plate or the lithium titanate battery electrode plate obtained by the preparation method of the lithium titanate battery electrode plate.
The lithium ion battery adopts the lithium titanate battery pole piece, the stability of the lithium ion battery is good, lithium titanate can not react with moisture to generate gas, the battery is not easy to bulge, and the stability and the safety are good. And the long-acting cycle performance of the lithium ion battery is good.
The following are specific examples.
Example 1:
the lithium titanate battery pole piece of the embodiment is prepared by the following steps:
(1) and (3) placing the flexible carbon cloth with the length of 8cm and the width of 5cm in 300mL of absolute ethyl alcohol for ultrasonic cleaning for 10 minutes, then drying in a vacuum oven at 85 ℃ for 45 minutes, taking out and placing in a sealed box.
(2) 47.5g of lithium titanate powder and 2.5g of graphite were weighed into a ball mill jar, the ratio of lithium titanate to graphite being 95: 5. Absolute ethanol was added to just submerge the powder and balls and the ball mill jar was run on a ball mill at 300rpm for 10 hours. Then the mixed powder is placed at 120 ℃ for vacuum drying for 5 h.
(3) A copper disc with the diameter of 60mm is taken as a tray of the target, 5g of graphite is flatly paved at the bottom of the tray, and the mass ratio of the graphite to the mixed powder is 1: 10. And then, uniformly spreading 50g of mixed powder on the graphite layer, and performing unidirectional dry pressing by using 6 tons of pressure to obtain the composite powder target.
(4) Placing the carbon-based current collector in a magnetron sputtering instrument, and taking the composite powder target as sputteringAnd (5) performing magnetron sputtering on the shot material. The process is as follows: the sputtering chamber is vacuumized to 5.0 x 10 of pressure-4After Pa, the temperature is raised to 400 ℃ at the heating rate of 30 ℃/min, 99.999 percent of high-purity argon is introduced as sputtering gas, the air pressure is adjusted to 0.3Pa, pre-sputtering is started after the target position is adjusted to 10cm, and the pre-sputtering time is 15min, so that impurities such as an oxide layer on the surface of the target material are cleaned. And after the pre-sputtering is finished, opening the baffle plate to carry out formal sputtering. Experimental parameters for the formal sputtering were set as follows: the sputtering power is 500W, the distance between the target and the substrate is 5.0cm, the working air pressure is 2Pa, the rotating speed of the substrate is 10r/min, the sputtering time is 4h, and the temperature of the substrate is 400 ℃. And (3) after the sputtering is finished, closing the substrate for heating, naturally cooling the substrate along with the cavity, keeping introducing gas, closing the gas until the temperature of the substrate is reduced to 100 ℃, and taking out the substrate when the temperature of the substrate is completely reduced to room temperature to obtain the lithium titanate battery pole piece of the embodiment.
Comparative example 1:
the lithium titanate battery pole piece of the comparative example is prepared by a slurry coating method.
47.5g of lithium titanate, 2.5g of graphite, 1.6g of sodium carboxymethyl cellulose as a binder and 5g of deionized water are uniformly stirred to obtain lithium titanate slurry. And coating lithium titanate slurry on the surface of clean flexible carbon cloth with the length of 8cm and the width of 5cm, and drying at 70 ℃ to obtain the lithium titanate electrode slice of the comparative example.
Comparative example 2:
the lithium titanate battery pole piece of the comparative example is prepared by a hydrothermal growth method.
Dropwise adding n-butyl titanate into a mixed solution of distilled water and concentrated hydrochloric acid, transferring the mixed solution into a reaction kettle, adding flexible carbon cloth, carrying out hydrothermal treatment at 180 ℃ for 24 hours to synthesize titanium dioxide growing on the flexible carbon cloth, then respectively carrying out ultrasonic washing for 5 minutes by using ethanol and distilled water, carrying out vacuum drying, dropwise adding a methanol solution of lithium hydroxide, carrying out vacuum drying, placing in a tubular furnace, and calcining at 800 ℃ in an argon atmosphere to obtain the lithium titanate battery pole piece.
Comparative example 3:
the lithium titanate battery pole piece of the comparative example is prepared by the following steps:
(1) and (3) placing the flexible carbon cloth with the length of 8cm and the width of 5cm in 300mL of absolute ethyl alcohol for ultrasonic cleaning for 10 minutes, then drying in a vacuum oven at 85 ℃ for 45 minutes, taking out and placing in a sealed box.
(2) 47.5g of lithium titanate powder and 2.5g of graphite were weighed into a ball mill jar, the ratio of lithium titanate to graphite being 95: 5. Absolute ethanol was added to just submerge the powder and balls and the ball mill jar was run on a ball mill at 300rpm for 10 hours. Then the mixed powder is placed at 120 ℃ for vacuum drying for 5 h.
(3) Taking a copper disc with the diameter of 60mm as a tray of the target, uniformly spreading 50g of mixed powder on a graphite layer, and performing unidirectional dry pressing by using 6 tons of pressure to obtain the composite powder target.
(4) And (3) placing the carbon-based current collector in a magnetron sputtering instrument, and performing magnetron sputtering by taking the composite powder target as a sputtering material. The process is as follows: the sputtering chamber is vacuumized to 5.0 x 10 of pressure-4After Pa, the temperature is raised to 400 ℃ at the heating rate of 30 ℃/min, 99.999 percent of high-purity argon is introduced as sputtering gas, the air pressure is adjusted to 0.3Pa, pre-sputtering is started after the target position is adjusted to 10cm, and the pre-sputtering time is 15min, so that impurities such as an oxide layer on the surface of the target material are cleaned. And after the pre-sputtering is finished, opening the baffle plate to carry out formal sputtering. Experimental parameters for the formal sputtering were set as follows: the sputtering power is 500W, the distance between the target and the substrate is 5.0cm, the working air pressure is 2Pa, the rotating speed of the substrate is 10r/min, the sputtering time is 4h, and the temperature of the substrate is 400 ℃. And (3) closing the substrate after sputtering is finished, naturally cooling the substrate along with the cavity, keeping introducing gas, closing the gas when the temperature of the substrate is reduced to 100 ℃, and taking out the substrate when the temperature of the substrate is completely reduced to room temperature to obtain the lithium titanate battery pole piece of the comparative example.
Through tests, in the lithium titanate battery pole pieces prepared in the above example 1 and the comparative examples 1 to 3, the thickness of the active material layer containing lithium titanate is 60 μm.
And (3) performance testing:
the lithium titanate battery pole pieces of the embodiment 1 and the comparative examples 1 to 3 are respectively assembled into a soft package battery and three electrodes for electrochemical tests, wherein the positive pole piece adopts an NCM pole piece, and the electrolyte, the diaphragm, the aluminum plastic film and other materials are conventional materials in the manufacture of the soft package battery.
1. And (3) rate performance test:
the test method comprises the following steps: and (3) respectively carrying out charging and discharging at a current of 0.5C/1C/2C/5C, and testing the discharge capacity of the lithium titanate negative electrode. The test results are shown in Table 1.
Table 1 discharge capacity of lithium titanate negative electrode
2. And (3) testing the cycle performance:
the test method comprises the following steps: and carrying out charge-discharge cycle test on the cycle performance of the lithium titanate cathode by using a current of 0.5C. The test results are shown in Table 2.
TABLE 2 cycling performance of lithium titanate negative electrodes
| Sample (I) | First-cycle discharge capacity | 300-ring discharge capacity | Capacity retention rate |
| Example 1 | 161mAhg-1 | 159mAhg-1 | 98.75％ |
| Comparative example 1 | 158mAhg-1 | 132mAhg-1 | 83.5％ |
| Comparative example 2 | 160mAhg-1 | 141mAhg-1 | 88.1％ |
| Comparative example 3 | 162mAhg-1 | 145mAhg-1 | 89.5％ |
3. Gas expansion test
The test method comprises the following steps: before and after the cycle performance test, the volume of the assembled soft package battery is recorded by adopting a drainage method, and the volume of the initial soft package battery before the test is recorded as V1And the volume of the soft package battery after 300 cycles is recorded as V2And calculating the volume change quantity of the soft package battery before and after the experiment, and recording the volume change quantity as the gas production volume V. The gas generation expansion condition of the lithium titanate negative electrode can be known according to the size of the gas generation volume V.
TABLE 3 gas generation expansion behavior of lithium titanate negative electrode
As can be seen from the data in tables 1 to 3, the lithium titanate negative electrode in example 1 has a higher discharge capacity and a good rate capability under the same conditions as the lithium titanate negative electrodes in comparative examples 1 to 3. The lithium titanate negative electrode of example 1 maintained the discharge capacity of 98.75% of the first cycle after 300 cycles of charge and discharge, and the cycling stability of the electrode was good. And after 300 cycles of charge and discharge, the battery of the embodiment 1 has less gas generation expansion and less gas generation volume than 1%, and compared with the batteries of the comparative examples 1-3, the battery has the advantages of remarkable improvement and higher stability and safety.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. A lithium titanate battery pole piece, comprising:
a current collector;
an active layer including an active material and a conductive agent; the active material is lithium titanate; the active layer is disposed on at least one surface of the current collector; and
and the conductive agent layer is arranged on the surface of the active layer and covers the active layer.
2. The lithium titanate battery pole piece of claim 1, wherein the current collector is selected from one of a metallic material and a flexible carbon-based material.
3. The lithium titanate battery pole piece of claim 2, wherein the flexible carbon-based material is selected from at least one of a carbon nanotube film, a conductive carbon cloth, a conductive carbon paper, and graphene foam.
4. The lithium titanate battery pole piece of claim 1, wherein the conductive agent in the active layer and the conductive agent layer are each independently selected from at least one of graphite, conductive carbon black, acetylene black, carbon nanotubes, and graphene.
5. The lithium titanate battery pole piece as claimed in claim 1, wherein in the active layer, the mass ratio of the active material lithium titanate to the conductive agent is (90-100): (0-10).
6. The lithium titanate battery pole piece of claim 1, wherein the mass ratio of the active layer to the conductive agent layer is (90-100): (1-10).
7. A preparation method of a lithium titanate battery pole piece is characterized by comprising the following steps:
sequentially forming a laminated active material layer and a conductive agent layer on the surface of a current collector by adopting a magnetron sputtering process; wherein the active layer includes an active material and a first conductive agent; the active material is lithium titanate; the conductive agent layer includes a second conductive agent.
8. The method for preparing the lithium titanate battery pole piece according to claim 7, wherein the step of sequentially forming the stacked active material layer and the conductive agent layer on the surface of the current collector by using a magnetron sputtering process comprises the steps of:
grinding and mixing the active material and the first conductive agent to obtain mixed powder;
sequentially adding the second conductive agent and the mixed powder into a die, and performing dry pressing to obtain a composite target material;
and putting the clean current collector into a magnetron sputtering instrument, and performing magnetron sputtering by taking the composite target material as a sputtering material so that the composite target material sequentially forms an active material layer and a conductive agent layer on the current collector.
9. Use of the lithium titanate battery electrode sheet according to any one of claims 1 to 6 or the lithium titanate battery electrode sheet obtained by the method of preparing a lithium titanate battery electrode sheet according to claim 7 or 8 in the manufacture of a lithium ion battery.
10. A lithium ion battery is characterized in that a negative electrode plate of the lithium titanate battery is the lithium titanate battery electrode plate in any one of claims 1 to 6 or the lithium titanate battery electrode plate obtained by the preparation method of the lithium titanate battery electrode plate in claim 7 or 8.
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