CN117712282A - Dry method negative electrode plate, secondary battery and device - Google Patents
Dry method negative electrode plate, secondary battery and device Download PDFInfo
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- CN117712282A CN117712282A CN202311766092.XA CN202311766092A CN117712282A CN 117712282 A CN117712282 A CN 117712282A CN 202311766092 A CN202311766092 A CN 202311766092A CN 117712282 A CN117712282 A CN 117712282A
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- 238000000034 method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
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- 239000002041 carbon nanotube Substances 0.000 claims abstract description 63
- 239000006258 conductive agent Substances 0.000 claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
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- 238000001035 drying Methods 0.000 abstract description 8
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a dry method negative electrode plate, it includes negative electrode current collector and sets up the negative electrode material layer on this negative electrode current collector surface, and this negative electrode material layer includes the conductive agent, and this conductive agent includes the carbon nanotube, and wherein, the diameter of this carbon nanotube is 13nm ~ 100nm. The carbon nano tube can be uniformly dispersed in the pole piece under the condition of a dry process, large-area conductive agent agglomeration does not occur, the conductive carbon utilization rate is high, a dense conductive network can be formed, the pole piece has conductivity exceeding 10S/cm, and the pole piece has low impedance characteristic.
Description
Technical Field
The application relates to a dry-method negative electrode plate, in particular to a dry-method negative electrode plate, a secondary battery and a device, and belongs to the field of battery materials.
Background
The current processing technology of the electrode slice film is divided into a wet process and a dry process. The wet process is to mix active matter, adhesive and conducting agent in solvent to form slurry mixture with solid content of 40-60%, and the slurry mixture is coated onto solid sheet current collector, and the solvent is evaporated after stoving to eliminate solvent from electrode sheet film. The dry process has the advantages of low energy consumption and great cost, and the active material, the binder and the conductive agent are mixed, the mixture is fibrillated, the fibrillated material is formed into a dry electrode film, and then the dry electrode film is compounded with the solid current collector. However, unlike the wet process, the dry process has a limited dispersing ability.
Therefore, there is an urgent need to develop a novel dry cathode tab.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a dry-method negative electrode plate, a secondary battery and a device. The application enables the negative electrode plate comprising the conductive agent to show low impedance characteristics by selecting the conductive agent.
The first aspect of the application provides a dry-method negative electrode plate, which comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, wherein the negative electrode material layer comprises a conductive agent, and the conductive agent comprises carbon nano tubes, and the diameter of the carbon nano tubes is 13-100 nm.
A second aspect of the present application provides a secondary battery comprising the dry-process negative electrode tab described above.
A third aspect of the present application provides an apparatus comprising the above secondary battery.
The conductive agent can be uniformly dispersed in the pole piece under the condition of a dry process, large-area aggregation can not occur, the conductive carbon utilization rate is high, and a dense conductive network can be formed. Based on the above improvement, the negative electrode tab containing the conductive agent has a conductivity exceeding 10S/cm, exhibiting low impedance characteristics.
Detailed Description
For the purposes of clarity, technical solutions and advantages of the present application, the following will be described in further detail in connection with the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
For simplicity, this application discloses only a few numerical ranges specifically. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
Unless otherwise indicated, terms used in the present application have well-known meanings commonly understood by those skilled in the art. Unless otherwise indicated, the numerical values of the parameters set forth in this application may be measured by various measurement methods commonly used in the art (e.g., may be tested according to the methods set forth in the examples of this application).
The list of items to which the term "at least one of," "at least one of," or other similar terms are connected may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single component or multiple components. Item B may comprise a single component or multiple components. Item C may comprise a single component or multiple components.
The term "D/G ratio" refers to the peak area ratio of the D peak to the G peak of the carbon nanotube.
The term "dry process" refers to a process in which no or substantially no solvent is used in the formation of the electrode film. For example, the components of the active layer or electrode film, including the carbon material and binder, may comprise dry particles. The dry particles used to form the active layer or electrode film may be combined to provide a dry particle active layer mixture.
The present application is further described below in conjunction with the detailed description. It should be understood that these specific embodiments are presented by way of example only and are not intended to limit the scope of the present application.
The first aspect of the application provides a dry-method negative electrode plate, which comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, wherein the negative electrode material layer comprises a conductive agent, and the conductive agent comprises carbon nano tubes, and the diameter of the carbon nano tubes is 13-100 nm. If the diameter of the carbon nano tube is too large, the utilization rate of the carbon nano tube is low, so that the number of formed conductive networks is limited, namely the density of the conductive networks is low, and finally, the conductivity of the pole piece is poor, and the rate performance and the cycle performance of the battery are affected; if the diameter of the carbon nanotubes is too small, the dispersibility of the carbon nanotubes is poor, and a uniform conductive network cannot be formed at the pole piece level. The conductive agent provided by the application can form a complete conductive network in the dry electrode pole piece, and simultaneously has good dispersibility, so that the pole piece has high conductivity level and low impedance characteristic.
In some embodiments, the carbon nanotubes have a diameter of 13nm, 18nm, 23nm, 28nm, 33nm, 38nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, or any range therebetween. In some embodiments, the carbon nanotubes have a diameter of 13nm to 80nm.
In some embodiments, the D/G ratio of the carbon nanotubes is 0.5 to 1.4, and if the D/G ratio of the carbon nanotubes is too large, the degree of defects of the carbon nanotubes is high and the intrinsic electronic conductance thereof is weak; if the D/G ratio of the carbon nanotubes is too small, there are difficulties in the current production. In some embodiments, the carbon nanotubes have a D/G ratio of 0.5, 0.7, 0.9, 1.1, 1.3, 1.4, or any range therebetween; in some embodiments, the carbon nanotubes have a D/G ratio of 0.6 to 1.3.
In some embodiments, the carbon nanotubes have a length of 0.8 μm to 17 μm, and if the carbon nanotubes are too short, the ability of the carbon nanotubes to form a long-range conductive network is weak and the conductivity of the pole piece is limited; if the length of the carbon nanotubes is too long, the winding degree among the carbon nanotubes is strong, the dispersion difficulty is increased, and thus the uniformity of the conductivity of the pole piece can be affected. In some embodiments, the carbon nanotubes have a length of 0.8 μm, 4 μm, 8 μm, 12 μm, 16 μm, 17 μm, or any range therebetween; in some embodiments, the carbon nanotubes have a length of 8 μm to 15 μm.
In some embodiments, the conductive agent further comprises carbon black.
In some embodiments, the primary particle size of the carbon black is from 35nm to 60nm; in some embodiments, the primary particle size of the carbon black is 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, or any range therebetween; in some embodiments, the primary particle size of the carbon black is from 35nm to 55nm.
In some embodiments, the carbon black has an oil absorption value of 120mL/100g to 300mL/100g; in some embodiments, the carbon black has an oil absorption value of 120mL/100g, 150mL/100g, 180mL/100g, 210mL/100g, 240mL/100g, 270mL/100g, 300mL/100g, or any range therebetween.
In some embodiments, the carbon black has a specific surface area of 40 to 90m 2 /g; in some embodiments, the carbon black has a specific surface area of 40m 2 /g、50m 2 /g、60m 2 /g、70m 2 /g、80m 2 /g、90m 2 /g or any range therebetween.
In some embodiments, M Carbon black The carbon black accounts for 0 to less than or equal to M in mass content of the conductive agent Carbon black <100%; in some embodiments, M Carbon black 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98% or any range therebetween.
In some embodiments, the mass ratio of the carbon black to the carbon nanotubes is 1: 4-4: 1, a step of; in some embodiments, the mass ratio of the carbon black to the carbon nanotubes is 1: 4. 1:3. 1: 2. 1:1. 2: 1. 2: 3. 3: 1. 3: 2. 3: 4. 4:1 or any range therebetween; in some embodiments, the mass ratio of the carbon black to the carbon nanotubes is 1:3.5 to 3.5:1, a step of; in some embodiments, the mass ratio of the carbon black to the carbon nanotubes is 1: 3-1: 1.
in some embodiments, the negative electrode active material includes at least one of a carbon-based material and a silicon-based material; in some embodiments, the carbon-based material comprises at least one of artificial graphite and natural graphite.
In some embodiments, the binder comprises at least one of polytetrafluoroethylene and sodium carboxymethyl cellulose.
In some embodiments, the mass content of the anode active material is 95% to 98% based on the mass of the anode material layer; in some embodiments, the mass content of the anode active material is 95%, 96%, 97%, 98% or any range therebetween, based on the mass of the anode material layer.
In some embodiments, the conductive agent is present in an amount of 0.8% to 2.5% by mass based on the mass of the negative electrode material layer; in some embodiments, the conductive agent is present in an amount of 0.8%, 1.1%, 1.4%, 1.7%, 2.0%, 2.3%, 2.5% or any range therebetween, based on the mass of the negative electrode material layer.
In some embodiments, the mass content of the binder is 1.0% to 2.5% based on the mass of the negative electrode material layer; in some embodiments, the mass content of the binder is 1.0%, 1.3%, 1.6%, 1.9%, 2.2%, 2.5% or any range therebetween, based on the mass of the negative electrode material layer.
In some embodiments, the silicon-based material has a mass content of less than 15% based on the mass of the negative electrode active material; in some embodiments, the silicon-based material is present in an amount of less than 5% by mass based on the mass of the negative electrode active material.
The application provides a method for manufacturing a dry-method negative electrode plate, which comprises the following steps: a mixture is prepared by dry-mixing a negative electrode active material, a dried conductive material, and a dried binder, and a high shear force is applied to the mixture. The mixture is disposed on a current collector and the current collector on which the mixture is disposed is rolled.
In some embodiments, the method of preparing a dry negative electrode tab of the present application is a dry method without using a solvent and includes: preparing a mixture by dry mixing a negative active material, a dried conductive material, and a dried binder, wherein the dried conductive material is carbon nanotubes or a combination of carbon nanotubes and carbon black, and the dried binder is polytetrafluoroethylene; applying a high shear force of 50N to 1000N to the mixture so that a mixture of particles in which the dried conductive material, the anode active material, and the dried binder are aggregated together is formed; the mixture is disposed on a current collector and the current collector on which the mixture is disposed is rolled.
A second aspect of the present application provides a secondary battery comprising the above dry-process negative electrode tab and positive electrode tab.
A third aspect of the present application provides an apparatus comprising the above secondary battery.
In some embodiments, the negative electrode tab includes a negative electrode material layer including a negative electrode active material including a carbon-based material, or a mixture of a carbon-based material and at least one material selected from a silicon-based material, a tin-based material, a phosphorus-based material, and metallic lithium.
In some embodiments, the silicon-based material includes at least one of silicon, a silicon alloy, a silicon oxygen compound, and a silicon carbon compound. In some embodiments, the carbon-based material comprises at least one of graphite, soft carbon, hard carbon, carbon nanotubes, and graphene. In some embodiments, the tin-based material includes at least one of tin, tin oxide, and tin alloy. In some embodiments, the phosphorus-based material includes phosphorus and/or a phosphorus complex.
In some embodiments, the negative electrode material layer further includes a binder. In some embodiments, the binder includes, but is not limited to: polytetrafluoroethylene (PTFE), polyolefins, polyethers, styrene-butadiene, polysiloxanes and copolymers of polysiloxanes, branched polyethers, polyvinyl ethers, copolymers thereof and/or mixtures thereof.
In some embodiments, the negative electrode further comprises a negative electrode current collector comprising: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or any combination thereof. The secondary battery of the present application also includes an electrolyte, which in some embodiments includes a lithium salt and a solvent.
In some embodiments, the secondary battery is a lithium secondary battery or a sodium secondary battery. In some embodiments, lithium secondary batteries include, but are not limited to: lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries.
In some embodiments, the secondary battery may include an outer package, which may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The soft bag can be made of one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.
In some embodiments, the shape of the secondary battery is not particularly limited, and may be cylindrical, square, or any other shape.
In some embodiments, the present application also provides a battery module. The battery module includes the secondary battery described above. The battery module of the present application employs the above-described secondary battery, and thus has at least the same advantages as the secondary battery. The number of secondary batteries contained in the battery module of the present application may be plural, and the specific number may be adjusted according to the application and capacity of the battery module.
In some embodiments, the present application also provides a battery pack including the above battery module. The number of battery modules included in the battery pack may be adjusted according to the application and capacity of the battery pack.
The present application also provides an apparatus comprising at least one of the above secondary battery, battery module or battery pack.
In some embodiments, the apparatus includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric storage systems, and the like. In order to meet the high power and high energy density requirements of the device for the secondary battery, a battery pack or a battery module may be employed.
In other embodiments, the device may be a cell phone, tablet, notebook, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
The conductive agents in the following examples and comparative examples are commercially available.
Examples and comparative examples
Example 1
Preparing a negative electrode plate: the artificial graphite, polytetrafluoroethylene and conductive agent are mixed, dispersed and fibrillated into a film in 98.0 wt%, 1.2 wt% and 0.8 wt%, and then the film is thermally compounded with the carbon coated copper foil to prepare the negative electrode plate.
Preparation of CR2016 type button half-cell: taking a metal lithium sheet as a counter electrode; in 1M LiPF 6 EC: DEC: DMC (1:1:1) is electrolyte; a polypropylene microporous membrane model 2400 Celgard is used as a diaphragm. All cells were assembled in a glove box filled with Ar gas.
And preparing four parallel sample electrode plates according to the mass ratio, detecting conductivity, detecting each sample for 3 times, taking an average value, and assembling the sample electrode plates into a button half-cell to test the impedance value. The model of the battery test equipment is Land CT 2001A, the voltage window is 0.005V-1.5V, and the pole piece load capacity is 13+/-0.1 g/cm 2 。
Examples 2 to 10 and comparative examples 1 to 5
Examples 2 to 10 and comparative examples 1 to 5 were achieved by adjusting the composition, content and characteristic parameters (e.g., primary particle diameter, diameter of carbon nanotubes, D/G ratio of carbon nanotubes, etc.) of the conductive agent on the basis of example 1, and specific adjustment measures and detailed data are shown in table 1.
Test method
1. Testing parameters of conductive agent
(1) Determination of diameter of carbon nanotubes
Firstly, dispersing a carbon nano tube sample, and then placing the carbon nano tube sample on a special micro grid of a transmission electron microscope and correctly storing the carbon nano tube sample; secondly, observing the hollow structure of the carbon nanotube by using a transmission electron microscope, and acquiring 5 TEM effective field images; finally, the diameter of the carbon nanotube sample is measured and counted by analyzing all effective field images of the same carbon nanotube sample, and the average value is obtained.
(2) Determination of the length of carbon nanotubes
Firstly, dispersing a carbon nano tube sample, then placing the dispersed carbon nano tube sample on an aluminum foil and correctly preserving the carbon nano tube sample; secondly, observing the tubular structure of the carbon nano tube by using a scanning electron microscope, and obtaining 3 SEM effective field images; finally, by analyzing all effective field images of the same carbon nanotube sample, measuring and counting the length of the carbon nanotube sample from beginning to end, and taking an average value.
(3) Determination of D/G ratio of carbon nanotubes
The test was performed using a microscope objective at 50 x magnification, a 532nm laser. And carrying out spectrum scanning on the sample area, and collecting 9 effective spectrums. And obtaining the peak area values of the D peak and the G peak by Lorentzian line type fitting, and taking the average value of 9 numbers after dividing.
(4) Determination of primary particle size of carbon black
Firstly, dispersing a carbon black sample, and then placing the carbon black sample on a special micro grid of a transmission electron microscope and correctly storing the carbon black sample; secondly, observing a primary structure of carbon black by using a transmission electron microscope, and acquiring 5 TEM effective field images; finally, the diameter of the primary structure of the carbon black sample is measured and counted by analyzing all effective field images of the same carbon black sample, and the average value is obtained.
(5) Determination of specific surface area of carbon black
See GB/T10722-2014.
(6) Determination of oil absorption value of carbon black
See GB/T3780.2-2007-carbon black-part 2: and (5) measuring the oil absorption value.
2. Battery performance test
(1) Determination of sheet volume resistivity
Rolling the middle strip of the whole pole piece to the target compaction density of 1.65+/-0.05 g/cm 3 4 circular pole pieces are cut by adopting a phi 14mm sheet punching machine, and the thickness of each pole piece is measured and recorded. And (3) carrying out resistivity test by using an RM2610 electrode resistance test system, measuring 3 points of each circular pole piece, and taking an average value of volume resistance of 12 points after the measurement is finished.
(2) Determination of pole piece interface resistivity
Rolling the middle strip of the whole pole piece to the target compaction density of 1.65±0.05g/cm 3 4 circular pole pieces are cut by adopting a phi 14mm sheet punching machine, and the thickness of each pole piece is measured and recorded. And (3) carrying out resistivity test by using an RM2610 electrode resistance test system, measuring 3 points of each circular pole piece, and taking an average value of interface resistances of 12 points after the measurement is finished.
(3) Determination of charge transfer impedance
Using blue electric test cabinet, discharging to 0.005V at 0.1C in 0.005V-1.5V voltage range at 25deg.C, standing for 5min, discharging to 0.005V at 0.05C, standing for 5min, charging to 1.5V at 0.1C, and discharging to 50% SOC at 0.1C after two cycles. Transfer to electrochemical workstation Autolab, test at 100000Hz-0.01Hz frequency range with amplitude 10 mV.
Test results
TABLE 1
As can be seen from table 1, the conductive agent satisfying the scope of the present application can form a complete conductive network in the dry electrode tab while exhibiting good dispersibility, giving the tab a high level of conductivity and low impedance characteristics.
While certain exemplary embodiments of the present application have been illustrated and described, the present application is not limited to the disclosed embodiments. Rather, one of ordinary skill in the art will recognize that certain modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application, as described in the appended claims.
Claims (10)
1. The dry-method negative electrode plate comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, wherein the negative electrode material layer comprises a conductive agent, and the conductive agent comprises carbon nanotubes, and the diameter of each carbon nanotube is 13-100 nm.
2. The dry negative electrode tab of claim 1, wherein the conductive agent further comprises carbon black.
3. The dry cathode pole piece according to claim 1 or 2, wherein the diameter of the carbon nanotubes is 13nm to 80nm.
4. The dry negative electrode tab according to claim 1 or 2, wherein the dry negative electrode tab satisfies at least one of the following conditions:
the D/G ratio of the carbon nano tube is 0.5-1.4, wherein the D/G ratio of the carbon nano tube refers to the peak area ratio of the D peak to the G peak of the carbon nano tube;
the length of the carbon nano tube is 0.8-17 mu m;
the mass content of the conductive agent is 0.8-2.5% based on the mass of the negative electrode material layer.
5. The dry negative electrode tab of claim 4, wherein the dry negative electrode tab satisfies at least one of the following conditions:
the length of the carbon nano tube is 8-15 mu m;
the D/G ratio of the carbon nano tube is 0.6-1.3.
6. The dry negative electrode tab of claim 2, wherein the dry negative electrode tab satisfies at least one of the following conditions:
the primary particle size of the carbon black is 35 nm-60 nm;
the oil absorption value of the carbon black is 120mL/100 g-300 mL/100g;
the specific surface area of the carbon black is 40m 2 /g～90m 2 /g；
The mass ratio of the carbon black to the carbon nano tube is 1: 4-4: 1.
7. the dry negative electrode tab of claim 6, wherein,
the mass ratio of the carbon black to the carbon nano tube is 1:3.5 to 3.5:1.
8. the dry cathode pole piece of claim 1, wherein the mass ratio of the carbon black to the carbon nanotubes is 1: 3-1: 1.
9. a secondary battery comprising the dry cathode tab of any one of claims 1-8.
10. An apparatus comprising the secondary battery according to claim 9.
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| CN202311766092.XA CN117712282A (en) | 2023-12-20 | 2023-12-20 | Dry method negative electrode plate, secondary battery and device |
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| CN202311766092.XA CN117712282A (en) | 2023-12-20 | 2023-12-20 | Dry method negative electrode plate, secondary battery and device |
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