CN113380978A - Flexible high-rate battery, pole piece and preparation method thereof - Google Patents
Flexible high-rate battery, pole piece and preparation method thereof Download PDFInfo
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- CN113380978A CN113380978A CN202110646501.7A CN202110646501A CN113380978A CN 113380978 A CN113380978 A CN 113380978A CN 202110646501 A CN202110646501 A CN 202110646501A CN 113380978 A CN113380978 A CN 113380978A
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- carbon nanotube
- active material
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 138
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 138
- 239000011149 active material Substances 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
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- 239000000843 powder Substances 0.000 claims description 5
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- 238000007599 discharging Methods 0.000 abstract description 7
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- 238000005452 bending Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 241001391944 Commicarpus scandens Species 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 239000010439 graphite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910000796 S alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
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- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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 provides a flexible high-rate battery, a pole piece and a preparation method thereof, wherein the pole piece comprises a current collector and an active material layer, and the active material layer is arranged on at least one side surface of the current collector; the active material layer comprises carbon nanotube bundles and active material particles, pores are formed among the carbon nanotubes in the carbon nanotube bundles, and the active material particles are distributed in the pores. The carbon nano tube improves the transmission capability of lithium ions and the rate capability of the battery in the charging and discharging process of the battery, improves the flexibility of the current collector, and has the operability of folding, bending and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a flexible high-rate battery, a pole piece and a preparation method thereof.
Background
With the rapid development of wearable electronic products, mobile portable electronic devices have penetrated into daily life. Some flexible electronic products have been brought out one after another, such as folding screen mobile phones, flexible smart bracelets, and the like, and a power supply system matched with the flexible electronic products is a prerequisite for realizing the applications of the smart wearable devices, and also needs to bear pressure, bending, pulling, rolling or even folding processing.
At present, flexible operation of the battery cannot be realized generally because a pole piece current collector is easy to break, so that the battery cannot be matched with a flexible electronic product.
Disclosure of Invention
The embodiment of the invention aims to provide a flexible high-rate battery, a pole piece and a preparation method thereof, and solves the problem that the battery in the prior art cannot realize flexible operation.
In order to achieve the above object, in a first aspect, an embodiment of the present invention provides a pole piece, including a current collector and an active material layer, where the active material layer is disposed on at least one side surface of the current collector; the active material layer comprises carbon nanotube bundles and active material particles, pores are formed among the carbon nanotubes in the carbon nanotube bundles, and the active material particles are distributed in the pores.
Optionally, the carbon nanotube bundle is an in-situ grown carbon nanotube bundle.
Optionally, an electrolyte is further included, the electrolyte being stored in the pores.
Optionally, the contact angle between the carbon nanotubes and the electrolyte is less than 5 °.
Optionally, the porosity of the carbon nanotube bundle is greater than 96%.
Optionally, the areal density of the pole piecesIs 1mg/cm2To 100mg/cm2。
In a second aspect, an embodiment of the present invention provides a battery, including a positive electrode tab, a separator and a negative electrode tab, where the positive electrode tab and/or the negative electrode tab is the tab provided in the first aspect of the embodiment of the present invention.
In a third aspect, an embodiment of the present invention provides a method for manufacturing a pole piece, where the method includes:
forming a current collector;
forming a carbon nanotube bundle on at least one side of the current collector, and spraying an active material slurry on the carbon nanotube bundle;
wherein the active material slurry includes an active material particle powder.
Optionally, the forming of the carbon nanotube bundle on at least one side of the current collector comprises:
forming the carbon nanotube bundle on at least one side of the current collector by using a vapor deposition in-situ growth method.
Optionally, the carbon nanotube bundle comprises an N-layer carbon nanotube bundle comprising a first carbon nanotube bundle and a second carbon nanotube bundle; the forming of the carbon nanotube bundle on at least one side of the current collector and spraying the carbon nanotube bundle with an active material slurry includes:
forming the first carbon nanotube bundle on at least one side of the current collector and spraying a portion of the active material slurry on the first carbon nanotube bundle;
forming the second carbon nanotube bundle on the first carbon nanotube bundle, and spraying a portion of the active material slurry on the second carbon nanotube bundle.
One of the above technical solutions has the following advantages or beneficial effects:
the embodiment of the invention provides a pole piece, a battery and a preparation method of the pole piece, wherein the pole piece is prepared by compounding and adhering a carbon nano tube cluster and an active material on the surface of a current collector, and the carbon nano tube cluster has strong conductivity and can improve the transmission capability and rate capability of lithium ions in the charging and discharging processes of the battery. Moreover, the carbon nanotube cluster has certain flexibility, and the carbon nanotube cluster is attached to the current collector, so that the flexibility of the current collector can be improved, the current collector is not easy to break, the current collector can bear bending or even folding operation, and the carbon nanotube cluster can be adaptively applied to various flexible electronic products.
Drawings
Fig. 1 is a schematic diagram of a pole piece according to an embodiment of the present invention;
fig. 2 is a flowchart of a method for manufacturing a pole piece according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, an embodiment of the invention provides a pole piece 100.
As shown in fig. 1, the pole piece 100 includes a current collector 10 and an active material layer 20, the active material layer 20 being provided on at least one side of the current collector 10; the active material layer 20 includes a carbon nanotube bundle 21 and active material particles 22, pores are formed between the carbon nanotubes in the carbon nanotube bundle 21, and the active material particles 22 are distributed in the pores.
In the embodiment of the present invention, the carbon nanotube bundle 21 is fluffy, that is, pores are formed between the carbon nanotubes in the carbon nanotube bundle, and the active material particles 22 are distributed in the pores, so that the carbon nanotube bundle 21 and the active material are compositely adhered to the current collector 10. Alternatively, in one embodiment, the areal density of the pole piece 100 is 1mg/cm2To 100mg/cm2。
The carbon nanotube bundle 21 has strong conductivity, and can improve the transmission capability and rate capability of lithium ions in the charging and discharging process of the battery, so that the lithium ion battery prepared based on the pole piece 100 has relatively excellent high-rate charging and discharging characteristics. Moreover, the carbon nanotube bundle 21 has a certain flexibility, and attaching the carbon nanotube bundle 21 to the current collector 10 can improve the flexibility of the current collector 10 without being easily broken, and can withstand bending or even folding operations. In addition, due to the conductive performance of the carbon nanotube cluster 21, when the active material particles are prepared, a conductive agent does not need to be added, and the manufacturing cost of the pole piece 10 can be reduced to a certain extent.
It should be noted that the electrode sheet 100 may be a positive electrode sheet, that is, the active material particles 22 are positive active material particles, the positive active material particles include but are not limited to one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel manganese cobaltate, lithium nickel manganese cobalt aluminate, lithium nickel cobaltate, and lithium-rich manganese, and the current collector 10 may be an aluminum foil. The electrode sheet 100 may also be a negative electrode sheet, that is, the active material particles 22 are negative active material particles including but not limited to one or more of lithium titanate, lithium powder, aluminum powder, metal oxide, artificial graphite, natural graphite, silicon alloy, sulfur alloy, and silicon carbon, and the current collector 10 may be a copper foil.
Optionally, the carbon nanotube bundle is an in-situ grown carbon nanotube bundle. In this embodiment, the fluffy carbon nanotube bundle 21 can be formed by growing the carbon nanotubes by an in-situ growth method.
Optionally, an electrolyte is further included, the electrolyte being stored in the pores.
During cycling of the cell, the electrolyte within the housing needs to be consumed. In this embodiment, pores are formed between the carbon nanotubes in the fluffy carbon nanotube bundle 21, and the pores can store the electrolyte and can supplement the electrolyte in the battery circulation process, so that the battery circulation performance is improved, and the battery life is prolonged.
Optionally, the contact angle between the carbon nanotubes and the electrolyte is less than 5 °.
In this embodiment, the contact angle between the carbon nanotube and the electrolyte may include two conditions: in the first case, the contact angle between the carbon nanotubes and the electrolyte stored in the pores; in the second case, the contact angle between the carbon nanotubes and the electrolyte injected into the battery case. The smaller the contact angle, the higher the wettability of the electrolyte, that is, the easier the electrolyte wets the carbon nanotubes, and the electrolyte consumed during the cyclic charge and discharge process is replenished, so that the charge and discharge effect of the battery is better, and the smaller the contact angle, the more electrolyte is stored in the pores. When the contact angle is smaller than 5 degrees, the wettability of the electrolyte is high, and the electrolyte which can be stored in the pores is more, so that the charging and discharging effects of the battery can be improved, the rate capability of the battery is improved, the cycle performance of the battery is further improved, and the service life of the battery is further prolonged.
Optionally, the porosity of the carbon nanotube bundle is greater than 96%.
In this embodiment, the carbon nanotube bundle has a high porosity, and the pores can contain more active material particles and electrolyte, so that the energy density of the battery can be improved, the cycle performance of the battery can be further improved, and the service life of the battery can be further prolonged.
In summary, the electrode plate provided by the embodiment of the invention is prepared by compounding and adhering the carbon nanotube bundle and the active material on the surface of the current collector, and the carbon nanotube bundle has strong conductivity, so that the transmission capability and rate capability of lithium ions in the charging and discharging processes of the battery can be improved. Moreover, the carbon nanotube cluster has certain flexibility, and the carbon nanotube cluster is attached to the current collector, so that the flexibility of the current collector can be improved, the current collector is not easy to break, the current collector can bear bending or even folding treatment, and the carbon nanotube cluster can be adaptively applied to various flexible electronic products.
The embodiment of the invention also provides a battery, which comprises a positive plate, a diaphragm and a negative plate, wherein at least one of the positive plate and the negative plate is the plate provided by the embodiment of the invention. It should be noted that the battery includes all technical features of the pole piece provided in the embodiment of the present invention, and can achieve all technical effects of the pole piece provided in the embodiment of the present invention, and in order to avoid repetition, details are not repeated herein.
Referring to fig. 2, fig. 2 is a flowchart of a method for manufacturing a pole piece according to an embodiment of the present invention.
As shown in fig. 2, the preparation method of the pole piece comprises the following steps:
wherein the active material slurry includes an active material particle powder.
In the embodiment, the carbon nanotube cluster and the active material are compounded and adhered to the surface of the current collector, and the strong conductivity of the carbon nanotube cluster can improve the transmission capability and rate capability of lithium ions in the charging and discharging processes of the battery. Moreover, the carbon nanotube cluster has certain flexibility, and the carbon nanotube cluster is attached to the current collector, so that the flexibility of the current collector can be improved, the current collector is not easy to break, the current collector can bear bending or even folding treatment, and the carbon nanotube cluster can be adaptively applied to various flexible electronic products.
In a specific implementation, in the case of preparing a positive plate, the current collector may be formed by an aluminum foil substrate, and the active material particles of the positive plate include, but are not limited to, one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel manganese cobaltate, lithium nickel manganese cobalt aluminate, lithium nickel cobalt oxide, and lithium-rich manganese; in the case of preparing the negative electrode sheet, the current collector may be formed of a copper foil substrate, and the active material particles of the negative electrode include, but are not limited to, one or more of lithium titanate, lithium powder, aluminum powder, metal oxide, artificial graphite, natural graphite, silicon alloy, sulfur alloy, and silicon carbon. It is to be noted that
Optionally, forming a bundle of carbon nanotubes on at least one side of the current collector comprises:
forming the carbon nanotube bundle on at least one side of the current collector by using a vapor deposition in-situ growth method.
In this embodiment, the carbon nanotubes grown by the high temperature vapor deposition in-situ growth method are fluffy, and the porosity may be greater than 96%. In specific implementation, the carbon nanotube bundle can be formed according to the following process:
1) dissolving ferrocene and thiophene into a solvent to obtain a mixed solution. The concentration of ferrocene in the mixed solution is 5 mg/mL-15 mg/mL, the concentration of thiophene is 1 muL/mL-5 muL/mL, and the solvent comprises methanol and n-hexane, wherein the volume ratio of the methanol to the n-hexane is 4: 1-15: 1.
2) Introducing the mixed solution obtained in the step 1) into a cracking furnace for cracking reaction to obtain the carbon nano tube cluster. The temperature of the cracking reaction is 1000 ℃ to 1400 ℃, and the time is 1min to 30 min.
3) Depositing the carbon nano tube bundle obtained in the step 2) on a metal foil substrate with a wet surface in a stretching mode.
Further, the carbon nanotube bundle and the active material paste may be compositely adhered to the current collector in a "sandwich" structure. In one embodiment, the carbon nanotube bundle comprises an N-layer carbon nanotube bundle comprising a first carbon nanotube bundle and a second carbon nanotube bundle; the forming of the carbon nanotube bundle on at least one side of the current collector and spraying the carbon nanotube bundle with an active material slurry includes:
forming the first carbon nanotube bundle on at least one side of the current collector and spraying a portion of the active material slurry on the first carbon nanotube bundle;
forming the second carbon nanotube bundle on the first carbon nanotube bundle, and spraying a portion of the active material slurry on the second carbon nanotube bundle.
In a specific implementation, a first layer of fluffy carbon nanotube bundle, referred to herein as the first carbon nanotube bundle, may be grown on the surface of the metal foil substrate, and a portion of the active material slurry may be uniformly sprayed on the first carbon nanotube bundle. Then, a second layer of fluffy carbon nanotube bundles is grown on the first carbon nanotube bundles, wherein the second carbon nanotube bundles are represented as the second carbon nanotube bundles, and a part of the active material slurry is uniformly sprayed on the second carbon nanotube bundles. And then, repeating the steps to continuously grow a third layer of fluffy carbon nanotube cluster, a fourth layer of fluffy carbon nanotube cluster and the like until the thickness of the pole piece reaches a preset value and/or the surface density of the pole piece reaches a preset value.
Wherein the active material slurry is a slurry in which the active material particles are mixed with N-Methylpyrrolidone (NMP), and the solid content of the active material slurry is 20% to 60%. Optionally, the preset value of the thickness of the pole piece may be 5 μm to 500 μm, and the preset value of the areal density of the pole piece may be 1mg/cm2To 100mg/cm2。
An alternative battery preparation process in an embodiment of the invention is described below:
step one, preparing a positive plate and a negative plate.
The positive plate comprises a positive current collector and a positive active material layer carried on the surface of the positive current collector, the positive current collector is an aluminum foil base material, and the positive active material layer comprises a compound of carbon nano tube cluster and positive active particles. The negative plate comprises a negative current collector and a negative active material layer carried on the surface of the negative current collector, the negative current collector is a copper foil substrate, and the negative active material layer comprises a compound of carbon nano tube cluster and negative active particles.
The carbon nano tube cluster and active material particles of the anode and the cathode are compounded into a sandwich structure. For details of the preparation process of the carbon nanotube bundle and the compounding manner of the carbon nanotube bundle and the active material particles of the positive electrode and the negative electrode, reference may be made to the description in the above embodiments, and for avoiding repetition, no further description is given here.
And step two, assembling the battery.
And stacking and assembling the negative pole pieces, the diaphragm and the positive pole piece in sequence to form a battery cell monomer and welding the pole lugs. The number of the positive plates, the diaphragms and the negative plates in the battery core can be increased according to the requirement; any adjacent positive plate and negative plate need to be separated by a diaphragm, for example, the two surfaces of the outermost layer of the battery core are laminated by negative plates; or winding the negative plate, the diaphragm, the positive plate and the diaphragm into a roll core structure in an arrangement mode; the pole lugs are welded in an ultrasonic welding or laser welding mode. And finally, packaging the battery cell through an aluminum plastic film.
Step three, injecting electrolyte
Vacuum drying at 60-100 deg.C for 24 hr, and injecting electrolyte into glove box with water content less than 20ppm, wherein the electrolyte is high rate electrolyte.
Several specific examples and comparative examples of the present invention are described below.
Example 1
Step one, preparing a positive plate and a negative plate.
The positive plate comprises a positive current collector and a positive active material layer carried on the surface of the positive current collector, the positive current collector is an aluminum foil base material, the thickness of the positive current collector is 10 mu m, and the positive active material layer comprises a compound of a carbon nano tube cluster and positive active particle lithium cobaltate. The negative plate comprises a negative current collector and a negative active material graphite layer borne on the surface of the negative current collector, the negative current collector is a copper foil substrate and has the thickness of 6 mu m, and the negative active material layer comprises a compound of carbon nano tube cluster and negative active particle graphite.
The carbon nano tube cluster and active material particles of the anode and the cathode are compounded into a sandwich structure. Wherein the in-situ production temperature of the carbon nano tube cluster is 1200 ℃, the feeding rate is 1g/s, the porosity of the prepared carbon nano tube cluster is 96%, and the surface density of the prepared positive plate is 10mg/cm2The prepared negative plate has the surface density of 6mg/cm2. The specific processes for preparing the carbon nanotube bundle and the method for combining the carbon nanotube bundle with the active material particles of the positive and negative electrodes are described in the above embodiments, and are not repeated hereAnd will be described in detail.
And step two, assembling the battery.
And stacking and assembling the negative pole pieces, the diaphragm and the positive pole piece in sequence to form a battery cell monomer and welding the pole lugs. The number of the positive plates, the diaphragms and the negative plates in the battery core can be increased according to needs, and the battery core is of a single-layer battery structure; any adjacent positive plate and negative plate need to be separated by a diaphragm, for example, the two surfaces of the outermost layer of the battery core are laminated by negative plates; or winding the negative plate, the diaphragm, the positive plate and the diaphragm into a roll core structure in an arrangement mode; the pole lugs are welded in an ultrasonic welding or laser welding mode. And finally, packaging the battery cell through an aluminum plastic film.
Step three, injecting electrolyte
Vacuum drying at 65 deg.C for 24 hr, and injecting electrolyte into glove box with 18ppm water content, wherein the electrolyte is high rate electrolyte.
Example 2
Example 2 differs from example 1 in that: the in-situ production temperature of the carbon nanotube bundle is 1300 ℃, and the porosity of the prepared carbon nanotube bundle is 96.5%.
Example 3
Example 3 differs from example 1 in that: the in-situ production temperature of the carbon nanotube bundle is 1400 ℃, and the porosity of the prepared carbon nanotube bundle is 97%.
Example 4
Example 4 differs from example 1 in that: the in-situ production temperature of the carbon nanotube bundle is 1500 ℃, and the porosity of the prepared carbon nanotube bundle is 97.5%.
Example 5
Example 5 differs from example 1 in that: the prepared positive plate has the surface density of 15mg/cm2。
Example 6
Example 6 differs from example 1 in that: the prepared positive plate has the surface density of 18mg/cm2。
Example 7
Example 7 differs from example 1 in that: the prepared negative plate has the surface density of 10mg/cm2。
Example 8
Example 8 differs from example 1 in that: the prepared negative plate has the surface density of 8mg/cm2。
Example 9
Example 9 differs from example 1 in that: the positive active material layer comprises a composite of carbon nanotube bundles and positive ternary material particles.
Example 10
Example 10 differs from example 1 in that: the negative active material layer comprises a composite of carbon nanotube bundles and negative active particle lithium titanate.
Example 11
Example 11 differs from example 1 in that: baking the assembled battery in the second step at the temperature of 80 ℃, and drying for 24 hours in vacuum
Example 12
Example 12 differs from example 1 in that: after baking the battery, an electrolyte was injected into a glove box having a water content of 10 ppm.
Comparative example 1
Comparative example 1 differs from example 1 in that: the positive plate comprises a positive current collector and a positive active material layer carried on the surface of the positive current collector, the positive current collector is an aluminum foil base material, the thickness of the positive current collector is 10 mu m, and the positive active material layer comprises positive active particle lithium cobaltate. The negative plate comprises a negative current collector and a negative active material graphite layer borne on the surface of the negative current collector, the negative current collector is a copper foil substrate and has the thickness of 6 mu m, and the negative active material layer comprises negative active particle graphite.
TABLE 1 test results of examples 1 to 12 and comparative example 1
| Retention rate of 10C rate discharge capacity | 5C rate discharge capacity retention | |
| Example 1 | 72％ | 81％ |
| Example 2 | 75％ | 85％ |
| Example 3 | 75％ | 86％ |
| Example 4 | 75％ | 85％ |
| Example 5 | 70％ | 81％ |
| Example 6 | 71％ | 82％ |
| Example 7 | 73％ | 84％ |
| Example 8 | 73％ | 83％ |
| Example 9 | 75％ | 85％ |
| Example 10 | 74％ | 84％ |
| Example 11 | 71％ | 82％ |
| Example 12 | 73％ | 83％ |
| Comparative example 1 | 51％ | 68％ |
The batteries prepared in examples 1 to 12 and comparative example 1 were subjected to cycle life tests, and the corresponding test results are shown in table 1. As can be seen from table 1, the higher the porosity of the carbon nanotube bundle, the higher the cycle performance of the prepared battery.
It should be noted that, various optional implementations described in the embodiments of the present invention may be implemented in combination with each other or implemented separately, and the embodiments of the present invention are not limited thereto.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "left", "right", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation and a specific orientation configuration and operation, and thus, should not be construed as limiting the present invention. Furthermore, "first" and "second" 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 defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be directly connected or indirectly connected through an intermediate member, or they may be connected through two or more elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The embodiments described above are described with reference to the drawings, and various other forms and embodiments are possible without departing from the principle of the present invention, and therefore, the present invention should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the size and relative sizes of components may be exaggerated for clarity. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. The terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, components, and/or components, but do not preclude the presence or addition of one or more other features, integers, components, and/or groups thereof. Unless otherwise indicated, a range of values, when stated, includes the upper and lower limits of the range and any subranges therebetween.
While the preferred embodiments of the present invention have been described, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims (10)
1. A pole piece is characterized by comprising a current collector and an active material layer, wherein the active material layer is arranged on at least one side surface of the current collector; the active material layer comprises carbon nanotube bundles and active material particles, pores are formed among the carbon nanotubes in the carbon nanotube bundles, and the active material particles are distributed in the pores.
2. The pole piece of claim 1, wherein the carbon nanotube bundles are in-situ grown carbon nanotube bundles.
3. The pole piece of claim 1, further comprising an electrolyte stored in the pores.
4. The pole piece of claim 1, wherein the contact angle between the carbon nanotubes and the electrolyte is less than 5 °.
5. The pole piece of claim 1, wherein the carbon nanotube bundles have a porosity greater than 96%.
6. The pole piece of claim 1, wherein the pole piece has an areal density of 1mg/cm2To 100mg/cm2。
7. A battery comprising a positive electrode sheet, a separator and a negative electrode sheet, wherein the positive electrode sheet and/or the negative electrode sheet is the electrode sheet according to any one of claims 1 to 6.
8. A preparation method of a pole piece is characterized by comprising the following steps:
forming a current collector;
forming a carbon nanotube bundle on at least one side of the current collector, and spraying an active material slurry on the carbon nanotube bundle;
wherein the active material slurry includes an active material particle powder.
9. The method of claim 8, wherein forming the bundle of carbon nanotubes on the at least one side of the current collector comprises:
forming the carbon nanotube bundle on at least one side of the current collector by using a vapor deposition in-situ growth method.
10. The method of claim 8, wherein the carbon nanotube bundle comprises an N-layer carbon nanotube bundle comprising a first carbon nanotube bundle and a second carbon nanotube bundle; the forming of the carbon nanotube bundle on at least one side of the current collector and spraying the carbon nanotube bundle with an active material slurry includes:
forming the first carbon nanotube bundle on at least one side of the current collector and spraying a portion of the active material slurry on the first carbon nanotube bundle;
forming the second carbon nanotube bundle on the first carbon nanotube bundle, and spraying a portion of the active material slurry on the second carbon nanotube bundle.
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| WO2023169113A1 (en) * | 2022-03-07 | 2023-09-14 | 宁德新能源科技有限公司 | Secondary battery and electronic device |
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