CN113745447B - Construction method of pole piece with porous structure and lithium ion battery - Google Patents
Construction method of pole piece with porous structure and lithium ion battery Download PDFInfo
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- CN113745447B CN113745447B CN202110921180.7A CN202110921180A CN113745447B CN 113745447 B CN113745447 B CN 113745447B CN 202110921180 A CN202110921180 A CN 202110921180A CN 113745447 B CN113745447 B CN 113745447B
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- 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
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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
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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
- H01M4/139—Processes of manufacture
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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 the technical field of electrode plate preparation methods, in particular to a method for constructing a porous structure electrode plate and a lithium ion battery. The construction method of the pole piece with the porous structure comprises the steps of forming micelles by using a surfactant and slurry, and breaking the micelles by coating and drying, so that the porous structure is formed in the pole piece. The invention discovers that the ion diffusivity, the electric conductivity and the loading capacity of the pole piece can be obviously improved by utilizing the porous structure which is directionally and accurately introduced, so that the power performance and the energy density of the battery are improved; the method has the advantages of relatively simple process, higher production efficiency, saving a large amount of time and energy, effectively reducing the production cost of the pole piece with the porous structure and overcoming the defects of the existing preparation process of the pole piece with the porous structure.
Description
Technical Field
The invention relates to the technical field of electrode pole piece preparation methods, in particular to a porous structure pole piece construction method and a lithium ion battery.
Background
The hybrid electric vehicle battery should have high power input and output and fast charge and discharge performance, and at the same time, should have higher energy to improve the endurance mileage, which requires the hybrid electric vehicle battery to have both high power and high specific energy performance.
But at present, high specific energy and high power are difficult to be obtained simultaneously. High specific energy requires a higher loading of the pole pieces, and high loading causes slow ion and charge transport, reducing the power performance of the battery.
The research of the prior art shows that the pole piece with a porous structure can be constructed, and the structural parameters (such as the surface density, the porosity and the like) of the pole piece are reasonably controlled, so that the ion diffusivity and the ion conductivity of the pole piece are obviously improved while the loading capacity of the pole piece is improved, and the pole piece has higher energy density and power density.
For the pole piece with a porous structure, various construction methods are provided in the prior art. For example, CN201821169795.9 discloses constructing a porous structure pole piece by a mechanical punching manner; CN201110159883.7 discloses that a porous structure pole piece is constructed by mixing and cold-pressing a positive electrode material and an organic matter into a block and then sintering at a low temperature.
However, the preparation method of the pole piece with the porous structure is a two-step method, namely, the pole piece or the pole block is prepared firstly, and then the porous structure is constructed through post-processing treatment. The construction method has the problems of complex process, low production efficiency, time and energy waste and high production cost.
Disclosure of Invention
Aiming at the problems, the invention provides a novel method for constructing a pole piece with a porous structure and a lithium ion battery.
In a first aspect, the invention provides a method for constructing a pole piece with a porous structure by a one-step method.
The construction method of the pole piece with the porous structure comprises the steps of forming micelles by using a surfactant and slurry, and breaking the micelles by coating and drying, so that the porous structure is formed in the pole piece.
It is known that the surfactant is usually used in the slurry of the pole piece as a dispersant, and the function of the surfactant is to prevent the conductive agent from agglomerating so as not to affect the performance of the pole piece, such as the slurry coating process disclosed in CN 106953066A.
The invention discovers that micelle can be formed after the surfactant is added into the slurry through deep research on the property of the surfactant, and the micelle can be broken and volatilized in the drying process, so that pores are formed. By utilizing the discovery, the invention provides the invention concept of obtaining the pole piece with the porous structure by a one-step method.
Tests show that the porous structure introduced directionally and accurately can obviously improve the ion diffusivity, the electric conductivity and the loading capacity of the pole piece, so that the power performance and the energy density of the battery are improved; the method has the advantages of relatively simple process, higher production efficiency, saving a large amount of time and energy, effectively reducing the production cost of the pole piece with the porous structure and overcoming the defects of the existing preparation process of the pole piece with the porous structure.
Furthermore, the invention discovers that the ion diffusivity, the conductivity and the load factor of the pole piece are related to the porosity and the pore sequence of the porous structure, and the porosity and the pore sequence are related to the fracture degree of the micelle; therefore, the invention provides that the surfactant can be more uniformly dispersed in the slurry by regulating and controlling the matching relationship between the type of the surfactant and the addition amount of the surfactant and the slurry so as to obtain a regularly ordered porous structure; and meanwhile, the drying temperature is regulated and controlled to control the cracking degree of the micelle, so that higher porosity is obtained, the performance of the pole piece is improved, and various requirements of actual products are met.
The surfactant is not particularly limited in the present invention, and may be any surfactant commonly used in the art, such as a cationic surfactant, an anionic surfactant or a nonionic surfactant.
But in order to avoid introducing ionic impurities into the slurry and ensure the quality of the pole piece, the surfactant is preferably an anionic surfactant only containing lithium cations, a cationic surfactant of volatile ammonium salts or a nonionic surfactant.
Further preferably, the anionic surfactant containing only lithium ions is lithium dodecylsulfonate. The cationic surfactant of the ammonium salt is tetradecyl trimethyl ammonium fluoride. The nonionic surfactant is n-amyl alcohol.
Meanwhile, because the temperature of micelles formed by the surfactant after heating and blowing is different, the number of carbon atoms of the surfactant for the positive electrode slurry is not more than 20; for the anode slurry, the number of carbon atoms of the surfactant is preferably not more than 15.
The addition amount of the surfactant is 0.5-20 wt% of the total mass of the slurry. The addition amount of the surfactant is related to the type of the slurry. For positive electrode slurry with higher solid content, the addition amount of the surfactant is generally not more than 10wt%; for the negative electrode slurry, the addition amount of the surfactant is generally not more than 20wt%. Researches show that by reasonably controlling the matching relationship between the type and the addition amount of the surfactant and the type of the slurry, the porous pole piece with uniform pore distribution and higher porosity can be obtained after subsequent drying.
The positive electrode slurry is a conventional slurry for preparing at least one of a lithium iron phosphate pole piece, a lithium vanadium phosphate pole piece, a ternary material pole piece, a lithium manganate pole piece, a lithium cobaltate pole piece and a lithium-rich manganese-based pole piece.
The negative electrode slurry is a conventional slurry for preparing at least one of a graphite negative electrode plate, a lithium titanate electrode plate, a silicon negative electrode plate, a silicon alloy negative electrode plate, a graphite silicon composite electrode plate and a graphite silicon oxide composite electrode plate.
In the coating and drying process, the coating and drying temperature of the anode slurry is 90-130 ℃; for the negative electrode slurry, the coating and drying temperature is 70-110 ℃.
As one of the specific embodiments of the invention, the positive electrode slurry is lithium iron phosphate, the surfactant is lithium dodecyl sulfonate, the addition amount is 4-6%, and the coating and drying temperature is 100-120 ℃; the surface density of the obtained pole piece is 7-9mg/cm 2 。
As one of the specific embodiments of the invention, the anode slurry is a ternary material, the surfactant is tetradecyl trimethyl ammonium fluoride, the addition amount is 8-10wt%, and the coating and drying temperature is 110-130 ℃; (ii) a The surface density of the obtained pole piece is 20-22mg/cm 2 。
As one of the specific implementation modes of the invention, the cathode slurry is graphite, the surfactant is n-amyl alcohol, the addition amount is 2-4wt%, and the coating and drying temperature is 80-100 ℃; the surface density of the obtained pole piece is 3-5mg/cm 2 。
By adopting the matching relationship of the slurry and the surfactant and optimizing the drying temperature, the surfactant is uniformly dispersed and fully volatilized, and the obtained pole piece has a porous structure with more order and higher porosity.
In a second aspect, the invention also provides a pole piece with a porous structure prepared by the method.
The pole piece with porous structure is a positive pole piece, and the single-side surface density of the pole piece is 5-40mg/cm 2 。
The pole piece with the porous structure is a negative pole piece, and the single-side surface density of the pole piece is 3-32mg/cm 2 。
In a third aspect, the present invention also provides a lithium ion secondary battery, wherein the positive electrode and/or the negative electrode of the lithium ion secondary battery uses the above porous electrode sheet.
The invention has the following beneficial effects:
the invention firstly provides a method for preparing a pole piece with a porous structure by using a micelle method. By directionally and accurately introducing the porous structure, the ion diffusivity, the electric conductivity and the loading capacity of the pole piece can be obviously improved, and further the power performance and the energy density of the battery are improved. The method has the advantages of relatively simple process, higher production efficiency, saving a large amount of time and energy, and effectively reducing the production cost of the pole piece with the porous structure.
Drawings
FIG. 1 is a graph of 50C discharge 10s and 40C charge 10s at 50% SOC of the battery obtained in example 1.
FIG. 2 is a graph of 50C discharged 10s and 40C charged 10s at 50% SOC of the battery obtained in comparative example 1.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Each of the components in the following examples is commercially available.
Example 1
The embodiment provides a pole piece with a porous structure, which comprises the following steps:
(1) Preparing conventional slurry for preparing a lithium iron phosphate positive pole piece of a battery;
the concrete formula of the slurry is as follows:
lithium iron phosphate: conductive agent: binder =96.5wt%:1.5wt%:2.0wt%.
(2) In the slurry homogenizing process, adding a surfactant lithium dodecyl sulfonate with the mass of 5wt% of the slurry to form micelles;
(3) Coating the slurry which forms the micelle obtained in the step (2) on a pole piece, heating to 110 ℃ in the coating process to dry the slurry and simultaneously break and volatilize the micelle to form the positive pole piece with a porous structure, wherein the surface density of the pole piece is 7.2mg/cm 2 。
(4) Preparing conventional slurry for preparing a graphite negative electrode plate of a battery;
the concrete formula of the slurry is as follows: graphite: conductive agent: binder =95.5wt%:1.5wt%:3.0wt%.
(5) In the slurry homogenization process, adding a surfactant n-amyl alcohol with the weight percent of 3% of the slurry to form micelles;
(6) Coating the slurry formed into the micelle in the step (5) on a pole piece, heating to 90 ℃ in the coating process to dry the slurry and break and volatilize the micelle at the same time to form a negative pole piece with a porous structure, wherein the surface density of the pole piece is 3.8mg/cm 2 。
And assembling the prepared porous positive pole piece and the porous negative pole piece, and then a diaphragm, electrolyte, an electrode leading-out end and a shell into a lithium ion battery, and testing the power performance and the energy density of the battery.
Fig. 1 is a graph of the power performance of the above cell.
As can be seen from FIG. 1, the obtained lithium iron phosphate/graphite battery discharges for 10s at a current of 50C, and the voltage is more than 2.5V; charging at 40C for 10s, and voltage < 3.7V. The power performance is much better than that of comparative example 1.
Example 2
This embodiment provides a porous structure pole piece, the step is as follows:
(1) Preparing conventional slurry for preparing a battery ternary material positive pole piece;
the concrete formula of the slurry is as follows: ternary materials: conductive agent: binder =93.0wt%:4.5wt%:2.5wt%.
(2) Adding 10wt% of surfactant tetradecyl trimethyl ammonium fluoride into the slurry during homogenization to form micelles;
(3) Coating the slurry forming the micelle in the step (2) on a pole piece, and coatingIn the cloth process, the slurry is heated to 120 ℃ to dry the slurry and meanwhile the micelle is broken and volatilized to form a pole piece with a porous structure, and the surface density of the pole piece is 20.3mg/cm 2 。
(4) Preparing conventional slurry for preparing a graphite silicon oxide composite negative electrode plate of a battery;
the concrete formula of the slurry is as follows: graphite: silicon oxide: conductive agent: binder =63.0wt%:31.5wt%:1.5wt%:4.0wt%.
(5) In the slurry homogenizing process, no surfactant is added, and in the coating process, the slurry is dried by heating to 70 ℃, and the surface density of the pole piece is 11.8mg/cm 2 。
And assembling the prepared porous positive pole piece and negative pole piece, a diaphragm, electrolyte, an electrode leading-out end and a shell into a lithium ion battery, and testing the power performance and the energy density of the battery.
Comparative example 1
The comparative example provides a preparation method of a pole piece, and is different from the preparation method of example 1 in that a surfactant is not added into the positive pole slurry and the negative pole slurry.
The result shows that the obtained pole piece has low porosity and irregular pore structure because the surfactant is not added; fig. 2 is a graph of the power performance of a battery made therefrom. As can be seen from FIG. 2, the lithium iron phosphate/graphite battery discharges 10s at a current of 50C, and the voltage is lower than 2.5V; the charging is carried out for 2.8s at a current of 40C, namely, the upper limit voltage is 3.7V.
Compared with the battery made of the pole piece obtained in the example 1, the power performance and the energy density of the battery made of the pole piece obtained in the comparative example 1 are relatively low.
Comparative example 2
The comparative example provides a preparation method of a pole piece, which is different from the preparation method of the example 1 in the selection of a surfactant; in this comparative example, the surfactant added to the positive electrode slurry was fatty alcohol-polyoxyethylene ether (carbon number > 20).
The results show that pore formation is not desirable and impurities are introduced because the surfactant cannot be completely volatilized during the drying process. The test results show that the energy density of the battery prepared by using the pole piece obtained in comparative example 1 is reduced and the power performance is reduced compared with the battery prepared by using the pole piece obtained in example 1.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (6)
1. A method for constructing a pole piece with a porous structure is characterized in that a surfactant and slurry are utilized to form micelles, and the micelles are broken through coating and drying, so that the porous structure is formed in the pole piece;
controlling the cracking degree of the micelle by regulating the matching relationship between the type of the surfactant and the addition amount thereof and the slurry and regulating the drying temperature;
the surfactant is an anionic surfactant only containing lithium cations, a cationic surfactant of ammonium salts or a nonionic surfactant;
for the slurry is a positive electrode slurry, the number of carbon atoms of the surfactant is not more than 20;
for the slurry to be a negative electrode slurry, the number of carbon atoms of the surfactant is not more than 15;
the addition amount of the surfactant is 0.5-20 wt% of the total mass of the slurry;
when the slurry is the anode slurry, the addition amount of the surfactant is not more than 10% of the total mass of the slurry;
when the slurry is negative electrode slurry, the addition amount of the surfactant is not more than 20wt% of the total mass of the slurry;
in the coating and drying process, the coating and drying temperature of the anode slurry is 90-130 ℃; for the negative electrode slurry, the coating and drying temperature is 70-110 ℃.
2. The construction method of the porous structure pole piece according to claim 1, wherein the positive electrode slurry is a slurry for preparing at least one of a lithium iron phosphate pole piece, a lithium vanadium phosphate pole piece, a ternary material pole piece, a lithium manganate pole piece, a lithium cobaltate pole piece and a lithium-rich manganese-based pole piece;
the negative electrode slurry is used for preparing at least one of a graphite negative electrode plate, a lithium titanate electrode plate, a silicon negative electrode plate, a silicon alloy negative electrode plate, a graphite silicon composite electrode plate and a graphite silicon oxide composite electrode plate.
3. A pole piece with a porous structure obtained by the construction method of any one of claims 1-2.
4. The porous structure pole piece of claim 3, wherein the porous structure pole piece is a positive pole piece, and the single-sided surface density of the porous structure pole piece is 5-40mg/cm 2 。
5. The porous structure pole piece of claim 3, wherein the porous structure pole piece is a negative pole piece, and the single-sided surface density of the porous structure pole piece is 3-32mg/cm 2 。
6. A lithium ion secondary battery, characterized in that the positive electrode and/or the negative electrode of the lithium ion secondary battery is the porous electrode sheet of any one of claims 3 to 5.
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| CN103682284A (en) * | 2013-08-30 | 2014-03-26 | 香港应用科技研究院有限公司 | Composite material for anode of lithium ion battery and manufacture method thereof |
| CN103797613A (en) * | 2011-09-08 | 2014-05-14 | 日本瑞翁株式会社 | Slurry for secondary batteries |
| CN107431194A (en) * | 2015-04-23 | 2017-12-01 | 日本瑞翁株式会社 | Lithium ion secondary battery electrode adhesive composition, electrode slurry for lithium ion secondary battery composition, electrode for lithium ion secondary battery and lithium rechargeable battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007046042A (en) * | 2005-07-14 | 2007-02-22 | Furukawa Electric Co Ltd:The | Method for producing porous structure, and porous structure obtained from the compound method |
| JP2011192615A (en) * | 2010-03-16 | 2011-09-29 | Sanyo Electric Co Ltd | Manufacturing method of electrode for lithium secondary battery, electrode for lithium secondary battery, and lithium secondary battery |
| CN106953066B (en) * | 2017-03-31 | 2020-02-14 | 广东永邦新能源股份有限公司 | Coating process of anode slurry |
| CN111224062A (en) * | 2020-01-14 | 2020-06-02 | 广州鹏辉能源科技股份有限公司 | Electrode plate and manufacturing method thereof |
| CN112687836B (en) * | 2020-12-25 | 2022-09-06 | 惠州亿纬锂能股份有限公司 | Coating method for lithium battery pole piece |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004079276A (en) * | 2002-08-13 | 2004-03-11 | Sony Corp | Positive electrode activator and its manufacturing method |
| CN103797613A (en) * | 2011-09-08 | 2014-05-14 | 日本瑞翁株式会社 | Slurry for secondary batteries |
| CN103682284A (en) * | 2013-08-30 | 2014-03-26 | 香港应用科技研究院有限公司 | Composite material for anode of lithium ion battery and manufacture method thereof |
| CN107431194A (en) * | 2015-04-23 | 2017-12-01 | 日本瑞翁株式会社 | Lithium ion secondary battery electrode adhesive composition, electrode slurry for lithium ion secondary battery composition, electrode for lithium ion secondary battery and lithium rechargeable battery |
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