CN115425227A - Additive for battery and preparation method and application thereof - Google Patents
Additive for battery and preparation method and application thereof Download PDFInfo
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- CN115425227A CN115425227A CN202211123154.0A CN202211123154A CN115425227A CN 115425227 A CN115425227 A CN 115425227A CN 202211123154 A CN202211123154 A CN 202211123154A CN 115425227 A CN115425227 A CN 115425227A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an additive for a battery, a preparation method and application thereof. The additive for the battery is used for the battery pole piece, can improve the wettability and the liquid absorption performance of the pole piece, shorten the duration of a battery liquid injection procedure, improve the productivity and improve the consistency of the pole piece soaking electrolyte. Moreover, the additive for the battery has a large amount of gap storage electrolyte, can effectively improve the liquid retention capacity of the pole piece, enhances the lithium ion conduction, and thus effectively improves the performance of the battery.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to an additive for a battery, and a preparation method and application thereof.
Background
In order to meet the demand of future electromotion, especially the further development of mobile phone, computer, electric automobile industry and circulating energy system, the performance improvement of the lithium ion battery also faces a huge challenge. At present, the market not only has an increasing demand for lithium ion batteries, but also gradually increases the performance requirements of the lithium ion batteries, including the increase of battery capacity, the increase of energy density, the extension of cycle life, the shortening of charging time, and the like.
The common lithium ion battery is formed by assembling a positive plate, a negative plate, a diaphragm and electrolyte, and the quality of the plate directly influences the comprehensive performance of the lithium ion battery. At present, pole pieces of commercial lithium ion batteries are generally prepared by a wet process, namely, slurry is coated on the surface of a current collector and dried to form the pole pieces, wherein the slurry contains active substances, conductive additives, binders and the like, and the binders are divided into water-based binders and oil-based binders according to different solubilities. In order to obtain a lithium ion battery with better performance, one of effective methods is to adopt a battery pole piece with larger thickness, for example, CN110061222A discloses a preparation method and application of lithium battery slurry, a conductive agent is respectively added into glue solution and active material in batches to obtain conductive slurry and premix, the conductive slurry is added into the premix for kneading and vacuum defoaming to obtain the battery slurry; the battery slurry is used for preparing positive and negative pole pieces, particularly thick pole pieces, and has long service life and higher multiplying power charge-discharge performance. Besides preparing thick pole pieces, the methods for improving the properties of the pole pieces adopted in the industry also comprise the steps of increasing the proportion of active substances in slurry, increasing the compactness of the pole pieces and the like, so that the capacity and the energy density of the lithium ion battery are increased. However, the pole piece with high energy density usually has the problem of poor wettability, so that the electrolyte is difficult to wet, the ion transmission is hindered, a lithium metal precipitation phenomenon is generated after the pole piece is used, and the cycle performance, the rate capability and the safety of the battery are seriously reduced.
In order to improve the wettability and the liquid retention performance of the pole piece, researchers propose a method for adding a liquid retention agent into slurry, for example, CN113571673A discloses a preparation method of a negative pole piece, which specifically comprises the following steps: dry-mixing the negative active material, the carbon black and the suspending agent, adding the binder, the liquid retention agent and the solvent, and uniformly mixing and stirring to prepare negative slurry; and coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode plate with the thickness of more than 200 mu m. The liquid retention agent in the negative electrode slurry is one of polyoxyethylene, polyethylene glycol, polyvinylpyrrolidone, polyacrylate and polystyrene, and compared with a common electrode plate, the addition of the liquid retention agent can improve the wettability and the liquid retention property to a certain extent, but the effect is limited, and the problem of the cycle performance of the electrode plate and a battery cannot be well solved.
The influence of the battery pole piece on the performance of the lithium ion battery is also reflected in the manufacturing process. In the production process of the lithium ion battery, one process is to inject electrolyte into the battery. The liquid injection process is an important process in the production of the lithium ion battery, and the consistency and the production efficiency of the lithium ion battery are directly determined by the precision of the liquid injection amount and the liquid injection efficiency. At present, the wettability of a pole piece is poor, the liquid absorption efficiency is low due to factors such as winding, lamination and extrusion, liquid injection needs a long time, the situation of uneven liquid absorption is easy to occur, and the production efficiency and the yield of a battery are seriously influenced. Meanwhile, the electrolyte consumption speed in the battery circulation process is high due to the limited liquid retention capacity of the pole piece, so that the battery has poor circulation performance.
Therefore, the improvement of the wettability of the pole piece and the liquid absorption and retention capacity of the pole piece is a research focus in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the additive for the battery, the preparation method and the application thereof, the additive for the battery has good affinity to electrolyte, larger specific surface area and good swelling performance, and can be used in a battery pole piece to remarkably improve the liquid absorption capacity and the liquid retention capacity of the pole piece, thereby improving the cycle performance of the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an additive for a battery, which is a secondary particle formed of latex primary particles.
The additive for the battery is secondary particles formed by aggregating latex primary particles, has good affinity with electrolyte, and has larger specific surface area and good swelling performance. The additive for the battery is used in the battery pole piece, so that the liquid absorption performance of the pole piece is improved, the time of a battery liquid injection procedure is shortened, and the productivity is improved; meanwhile, the wettability of the pole piece is improved, so that the consistency of the pole piece in soaking the electrolyte is improved. Moreover, the secondary particles have higher specific surface area and good swelling performance, have a large amount of gaps for storing electrolyte, can improve the liquid retention capacity of the pole piece, enhance the lithium ion conduction, and thus effectively improve the cycle performance of the battery.
Preferably, the battery additive is a pole piece additive, and more preferably a negative electrode additive.
Preferably, the secondary particles have a particle size of 0.5 to 100.0 μm, and may be, for example, 1.0 μm, 3.0 μm, 5.0 μm, 8.0 μm, 10.0 μm, 15.0 μm, 20.0 μm, 25.0 μm, 30.0 μm, 35.0 μm, 40.0 μm, 45.0 μm, 50.0 μm, 55.0 μm, 60.0 μm, 65.0 μm, 70.0 μm, 75.0 μm, 80.0 μm, 85.0 μm, 90.0 μm, or 95.0 μm, and specific dot values therebetween, which are limited in terms of space and for the sake of brevity, and the present invention is not exhaustive of the specific dot values included in the ranges.
Preferably, the specific surface area of the secondary particles is more than or equal to 10m 2 A value of,/g, for example, 15m 2 /g、20m 2 /g、25m 2 /g、30m 2 /g、50m 2 /g、80m 2 /g、100m 2 /g、200m 2 /g、300m 2 /g、350m 2 /g、400m 2 /g、450m 2 /g、500m 2 /g、550m 2 /g、600m 2 /g、650m 2 /g、700m 2 /g、750m 2 /g、800m 2 /g、850m 2 /g、900m 2 (ii)/g or 950m 2 And/g, etc.
As a preferable technical scheme of the invention, the particle size of the secondary particles is 0.5-100 mu m, and the specific surface area is more than or equal to 10m 2 The electrolyte solution is used as an additive for the battery pole piece, can improve the wetting property of the pole piece and the liquid absorption performance of the pole piece, has a large amount of gaps for storing electrolyte, and improves the liquid retention capacity of the battery pole piece. If the particle diameter of the secondary particles is too small or too largeIf the surface area is too low, the electrolyte is difficult to swell and store, so that the liquid absorption and retention performance of the pole piece are affected; if the particle size of the secondary particles is too large, coating processing of the pole piece may be abnormal.
Preferably, the secondary particles have a swelling ratio of 100% to 10000%, which may be, for example, 200%, 300%, 500%, 700%, 900%, 1000%, 2000%, 3000%, 4000%, 5000%, 6000%, 7000%, 8000% or 9000%, and the specific points between the above points, which are not exhaustive for the sake of brevity and simplicity, are included in the scope of the present invention.
Illustratively, the swelling ratio refers to the mass change rate of the secondary particles after soaking in the electrolyte at 85 ℃ for 24 hours.
Preferably, the latex primary particles are polymer latex primary particles.
Preferably, the latex primary particles include any one of or a combination of at least two of styrene-acrylic latex particles, styrene-butadiene latex particles, pure acrylic latex particles, nitrile-butadiene latex particles, vinyl acetate-acrylic latex particles, silicone-acrylic latex particles, polyvinylidene fluoride latex particles, or polytetrafluoroethylene latex particles.
Preferably, the primary latex particles have a particle size of 20-600nm, such as 40nm, 60nm, 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm, 480nm, 500nm, 520nm, 550nm or 580nm, and the specific values therebetween are limited for the sake of brevity and brevity, and the invention is not intended to be exhaustive of the specific values included in the range, and more preferably 50-400nm.
In a second aspect, the present invention provides a method for preparing the additive for a battery according to the first aspect, the method comprising: and spray-drying the polymer emulsion to form secondary particles to obtain the battery additive.
Preferably, the polymer emulsion comprises any one of or a combination of at least two of styrene-acrylic emulsion, styrene-butadiene emulsion, pure acrylic emulsion, butyronitrile emulsion, vinyl acetate-acrylic emulsion, silicone-acrylic emulsion, polyvinylidene fluoride emulsion or polytetrafluoroethylene emulsion.
Preferably, the polymer emulsion has a solids content of 30 to 80%, for example 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%, and the specific values between the above values, limited to space and for the sake of brevity, are not exhaustive of the specific values included in the ranges.
Preferably, the inlet temperature of the spray drying is in the range of 140 to 220 ℃, for example 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or 210 ℃, and specific values therebetween, for reasons of brevity and clarity, are not exhaustive of the invention to include specific values within the stated ranges.
Preferably, the outlet temperature of the spray drying is 70-110 ℃, for example 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or 105 ℃, and the specific values therebetween, are not exhaustive and for the sake of brevity.
Preferably, the pressure of the spray drying is 0.2-0.8MPa, and may be, for example, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa, 0.6MPa, 0.65MPa, 0.7MPa or 0.75MPa, and specific values therebetween, not to be limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the feeding speed of the polymer emulsion in the spray drying is 5-15mL/min, for example, 6mL/min, 7mL/min, 8mL/min, 9mL/min, 10mL/min, 11mL/min, 12mL/min, 13mL/min or 14mL/min, and the specific values therebetween are not exhaustive, and the invention is not exhaustive for the specific values included in the range for reasons of brevity and conciseness.
Preferably, the preparation method comprises: and introducing the polymer emulsion into a spray drying device at the speed of 5-15mL/min, and carrying out spray drying under the conditions that the pressure is 0.2-0.8MPa, the inlet temperature is 140-220 ℃ and the outlet temperature is 70-110 ℃ to form secondary particles, thus obtaining the battery additive.
In a third aspect, the present invention provides an electrode material composition comprising the additive for batteries according to the first aspect.
Preferably, the electrode material composition includes an electrode active material, a conductive agent, a binder, and the battery additive.
Preferably, the battery additive is 0.01 to 1.00 parts by mass, for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.10 parts, 0.20 parts, 0.30 parts, 0.40 parts, 0.50 parts, 0.60 parts, 0.70 parts, 0.80 parts, or 0.90 parts by mass based on 100 parts by mass of the electrode active material, and specific point values between the above-mentioned point values are not limited to space and are included in the range for brevity and clarity, and specific point values included in the range are not exhaustive in the present invention.
Preferably, the electrode active material is a positive electrode active material or a negative electrode active material.
Preferably, the positive active material includes an active material that can intercalate and deintercalate lithium, and exemplary include, but are not limited to: any one of lithium iron phosphate and lithium transition metal composite oxide (such as nickel-cobalt-manganese ternary material) or a combination of at least two of the above materials.
Preferably, the negative electrode active material includes any one of a carbon material, a silicon oxygen material, or a combination of at least two thereof.
Preferably, the carbon material comprises any one of graphite, carbon black, carbon nanotubes, carbon fibers, mesocarbon microbeads or petroleum coke, or a combination of at least two of them.
Preferably, the conductive agent comprises any one of carbon black, graphite, carbon nanotubes or carbon fibers or a combination of at least two thereof.
Preferably, the conductive agent is 0.1 to 5.0 parts by mass, for example, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1.0 part, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3.0 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4.0 parts, 4.2 parts, 4.5 parts, or 4.8 parts, based on 100 parts by mass of the electrode active material, and specific points between the above points are not listed again in the present invention for the sake of brevity and space and the range is not included in the specific points.
Preferably, the binder comprises polyvinylidene fluoride (PVDF) or Styrene Butadiene Rubber (SBR).
Preferably, the binder is 0.01 to 5.00 parts by mass, for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.10 parts, 0.30 parts, 0.50 parts, 0.70 parts, 0.90 parts, 1.00 parts, 1.20 parts, 1.50 parts, 1.80 parts, 2.00 parts, 2.20 parts, 2.50 parts, 2.80 parts, 3.00 parts, 3.20 parts, 3.50 parts, 3.80 parts, 4.00 parts, 4.20 parts, 4.50 parts, or 4.80 parts, based on 100 parts by mass of the electrode active material, and specific point values between the above-mentioned point values are not limited to the breadth and the present invention is not exhaustive, and specific point values included in the range are not listed for brevity.
Preferably, a thickening agent is further included in the electrode material composition.
Preferably, the thickener is sodium carboxymethyl cellulose (CMC).
Preferably, the thickener is 0.01 to 3.00 parts by mass, for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.10 parts, 0.30 parts, 0.50 parts, 0.70 parts, 0.90 parts, 1.00 parts, 1.20 parts, 1.50 parts, 1.80 parts, 2.00 parts, 2.20 parts, 2.50 parts, or 2.80 parts by mass based on 100 parts by mass of the electrode active material, and specific point values between the above point values, which are not exhaustive of the range included in the present invention for sake of brevity and simplicity.
Preferably, the electrode material composition is a negative electrode material composition including a negative electrode active material, a conductive agent, a binder, and the battery additive.
In a fourth aspect, the present invention provides a battery pole piece comprising a current collector and a coating disposed on the current collector, the material of the coating comprising the electrode material composition according to the third aspect.
Preferably, the battery pole piece is a negative pole piece.
As a preferred technical scheme of the invention, the electrolyte wettability of the negative pole piece containing the additive for the battery is good, the imbibition time of the negative pole piece is less than or equal to 20s, compared with the common negative pole piece, the imbibition time is reduced by more than 42%, the imbibition performance is excellent, the battery electrolyte injection process time is obviously shortened, and the productivity is improved. The negative pole piece containing the additive for the battery has excellent liquid absorption and retention performances, reduces the consumption of electrolyte in the battery circulation process, enhances the lithium ion conduction, enables the capacity retention rate of the lithium ion battery circulating for 100 weeks at normal temperature to be more than or equal to 98.0%, and has excellent circulation performance.
In a fifth aspect, the present invention provides an electrochemical energy storage device comprising at least one of the battery additive according to the first aspect, the electrode material composition according to the third aspect, and the battery pole piece according to the fourth aspect.
Preferably, the electrochemical energy storage device comprises any one of a lithium ion battery, a sodium ion battery, a supercapacitor, a fuel cell or a solar cell.
Compared with the prior art, the invention has the following beneficial effects:
the additive for the battery is secondary particles formed by aggregating latex primary particles, has good affinity with electrolyte, larger specific surface area and good swelling performance, and the specific surface area is more than or equal to 10m 2 (ii)/g, the swelling ratio is 200-10000%. The additive for the battery is used for the battery pole piece, can improve the wettability and the liquid absorption performance of the pole piece, shortens the duration of a battery liquid injection process, improves the capacity, and improves the consistency of the pole piece in the electrolyte. Moreover, the additive for the battery has a large amount of gap storage electrolyte, can improve the liquid retention capacity of the pole piece, enhances the lithium ion conduction, and thus effectively improves the cycle performance of the battery.
Drawings
FIG. 1 is a scanning electron micrograph of the secondary particles described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
"optionally" or "either" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Reference throughout this specification to "one embodiment," "some embodiments," "exemplarily," "a specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The polymer emulsions referred to in the following embodiments of the invention are all commercially available products, for example, styrene-acrylic, styrene-butadiene, acrylic, nitrile-butadiene, vinyl acetate, and polyvinylidene fluoride (PVDF) emulsions are available from Michelin.
In the following embodiment of the present invention, the viscosity of the polymer emulsion is measured by using an NDJ-5S digital rotational viscometer (Shanghai Ninhun Intelligent science and technology Co., ltd.), the measurement temperature is 25 ℃, and the viscosity of the binder is measured by using a number 1 rotor (rotation speed is 60 rpm) of the rotational viscometer. The particle size of the latex primary particles is obtained by testing with a Malvern particle size tester, and the testing quality is detected by using Expert advise (the size of samples under different concentrations is detected, and the particle size does not depend on the concentration of the samples). The spray drying apparatus was a spray dryer (model 5, changzhou ease).
Example 1
An additive for a battery and a preparation method thereof, wherein the additive for the battery is a secondary particle formed by primary latex particles (styrene-acrylic latex particles with the average particle size of 300 nm); the preparation method comprises the following steps:
1kg of a commercially available styrene-acrylic emulsion (solids content 40%, viscosity 20 cps) was spray-dried with the following parameters: the inlet temperature is 180 ℃, the outlet temperature is 90 ℃, the feeding speed of the styrene-acrylic emulsion is 10mL/min, and the air pressure is 0.5MPa; and after spraying is finished, collecting the particles which are secondary particles to obtain the additive for the battery.
Examples 2 to 10
An additive for a battery and a preparation method thereof are different from those of example 1 in that the process parameters of latex primary particles and/or spray drying are different, and are specifically shown in Table 1.
TABLE 1
Comparative example 1
One battery additive was a conventional styrene-acrylic latex particle, i.e., the primary latex particle of example 1.
Comparative example 2
An additive for a battery (a conventional liquid retention additive), specifically a methyl methacrylate-butadiene-styrene copolymer having a linear structure, has a number average molecular weight of 18 ten thousand.
Application examples 1-12, comparative application examples 1-2
A battery pole piece is a negative pole piece and comprises a current collector (Cu foil) and a coating arranged on the current collector, wherein the coating is made of an electrode material composition and comprises a negative active substance (a silica material SiO-450, new energy Material GmbH, silicon content 10%), a conductive agent (carbon black SP), a binder (styrene butadiene rubber, SBR), a thickening agent (sodium carboxymethylcellulose, CMC) and the battery additive, and the mass ratio of the negative active substance to the conductive agent to the binder to the thickening agent to the battery additive is 96; the additives for batteries were the additives for batteries provided in examples 1 to 12 and comparative examples 1 to 2, respectively.
The preparation method of the negative pole piece comprises the following steps: mixing a negative electrode active material, a conductive agent, a binder, a thickening agent and the battery additive according to a mass ratio of 96 4 And (4) rolling the N/m load per unit length to obtain the negative pole piece.
A lithium ion battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the negative pole piece is the negative pole piece; the preparation method of the lithium ion battery comprises the following steps:
(1) Preparing a positive pole piece: respectively mixing the lithium iron phosphate material serving as a positive electrode active material, conductive carbon black and a binder (PVDF) according to a solid content of 95.5 parts by mass 4 Rolling the N/m load per unit length to obtain a positive pole piece;
(2) Negative pole piece: as described hereinbefore;
(3) A diaphragm: a PE porous polymer film (Shenzhen star source material science and technology Limited) is adopted as a diaphragm;
(4) Assembling the lithium ion battery: winding the positive pole piece, the isolating film and the negative pole piece in sequence to obtain a battery core; and packaging the battery core by using an aluminum plastic film, baking to remove water, injecting electrolyte, and performing vacuum packaging, shelving, formation, secondary sealing, shaping and other processes to obtain the lithium ion battery.
Comparative application example 3
A battery pole piece and a lithium ion battery comprising the same are disclosed, wherein the battery pole piece is a negative pole piece, and the battery pole piece is only different from an application example 1 in that a material (an electrode material composition, namely negative electrode slurry) of a coating does not contain a battery additive; other materials, proportions and preparation methods were the same as in application example 1.
And (3) performance testing:
(1) Morphology and specific surface area of additive (secondary particle) for battery
The additive for cells (secondary particles) described in the examples was subjected to morphological tests using a scanning electron microscope (SEM, EVOMA25, ZEISS). Illustratively, the scanning electron microscope image of the secondary particles described in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the secondary particles have an average particle size of about 3 μm, are large-sized spherical particles formed by stacking small primary latex particles, and that the primary latex particles are not closely adhered to each other and have a large number of voids, which are helpful for storing the electrolyte.
Testing the particle size of the secondary particles by using a Malvern particle size tester, and detecting the testing quality by using an Expert advise (detecting the sizes of samples under different concentrations, wherein the particle size does not depend on the concentration of the samples); wherein, the grain diameter of the secondary particles in the embodiment 1 is 3.2 μm, which is matched with the result in the scanning electron microscope image of the figure 1; all particle size test data are shown in table 2.
The specific surface area of the porous latex particles is tested by adopting a multipoint BET method, a tester is a Michelson specific surface tester, and adsorbate is high-purity N 2 The obtained specific surface area data are shown in table 2.
(2) Swelling ratio of additive (secondary particle) for battery
Dispersing an additive for a battery to be tested in water to form uniform dispersion liquid, and dropwise adding the dispersion liquid into a clean die to ensure the solid content4g +/-0.1 g, drying in an oven at 70 ℃ for 12h, taking out cut pieces 1cm multiplied by 1cm, weighing the prepared sample, and recording the mass M 1 (ii) a A sufficient amount of electrolyte was weighed, added to a glass bottle containing the aforementioned sample to ensure complete immersion of the sample in electrolyte, and the bottle was sealed and placed in a 85 ℃ water bath for 24h. Taking out the sample, wiping the electrolyte on the sample with clean dust-free paper, weighing the mass of the swelled sample, and recording as M 2 。
Swelling ratio =100% × (M) 2 -M 1 )/M 1 The test results are shown in table 2.
(3) Liquid absorption performance of battery pole piece
And (3) dropwise adding 1mL of electrolyte DMC to the negative electrode plate to be detected, timing from the moment that the electrolyte DMC contacts the electrode plate to the moment that the electrolyte is completely absorbed by the electrode plate, and recording the liquid absorption time of the electrode plate, wherein the liquid absorption time is specifically shown in Table 2.
(4) Cycle performance of lithium ion batteries
Charging the prepared lithium ion battery to 4.2V at a constant current of 0.33C, then charging at a constant voltage to a cut-off current of 0.02C, and discharging to 2.5V at 0.33C; the sample was left for 5min, and then charged at a constant current of 0.33C to 4.2V, further charged at a constant voltage to an off current of 0.02C, and discharged at 0.33C to 2.5V, thereby carrying out initial adjustment.
Charging the lithium ion battery adjusted in the initial stage to 4.2V at a constant current of 0.5C at 25 ℃, then charging the lithium ion battery at a constant voltage to a cut-off current of 0.02C, standing for 5min, then discharging the lithium ion battery at a constant current of 1C to 2.5V, standing for 5min, and measuring the first cycle discharge capacity; after 100 cycles of this cycle, charge/discharge, the 100 th cycle discharge capacity was measured, and the 100 th cycle capacity retention ratio was calculated using the following formula:
capacity retention (%) of 100 cycles =100% × 100 th cycle discharge capacity/first cycle discharge capacity; the test results are shown in table 2.
TABLE 2
In table 2, "not added" in the last row is the test data of comparative application example 3, in which the negative electrode sheet does not use the battery additive, "-" represents the test data without particle size, specific surface area and swelling ratio.
As can be seen from the performance test data in Table 2, the secondary particles formed by aggregation of the additives for batteries as the primary latex particles provided by the present invention have a suitable particle size and a large specific surface area, and the particle size distribution of the secondary particles described in examples 1 to 6 is 1.1 to 47.4 μm and the specific surface area is 16.7 to 84.6m by adjusting and optimizing the spray drying process 2 Has good swelling performance and good affinity to electrolyte, and the swelling ratio is 200-9500%. The negative pole piece containing the additive for the battery has good infiltration consistency on electrolyte, excellent imbibition performance and imbibition time of 5-20s, and compared with the common negative pole piece without the additive (compared with application example 3), the imbibition time is shortened by more than 42%, so that the time of a battery liquid injection process is shortened, and the capacity is improved. Meanwhile, the additive for the battery has a large amount of gap storage electrolyte, can improve the liquid retention capacity of a pole piece, enhances the lithium ion conduction, enables the capacity retention rate of the lithium ion battery after being cycled for 100 weeks at normal temperature to be 98.0-99.5%, and obviously improves the cycle performance of the battery. Meanwhile, the aggregation structure, the appearance, the specific surface area and the property of the secondary particles can be adjusted and optimized by setting the particle size of the primary particles of the latex and adjusting the technological parameters of spray drying, so that the wettability of the pole piece, the liquid absorption performance and the liquid retention capacity of the pole piece can be more effectively improved by the additive for the battery; if the particle size of the latex primary particles exceeds the preferable range of the invention (examples 7-8), the specific surface area of the secondary particles is affected, and the performance of the pole piece and the lithium ion battery is further affected; if the technological parameters of spray drying are beyond the preferable range of the invention (examples 9-12), the morphology, specific surface area and particle size of the secondary particles are affected, and the improvement effect of the battery additive on the liquid absorption and liquid retention of the pole piece is poor.
According to the invention, by preparing the secondary particles with specific morphology, the battery additive can remarkably improve the wettability, the liquid absorption property and the liquid retention capacity of the pole piece, and the improvement effect on the performances of the pole piece and the lithium ion battery is far higher than that of a common latex primary particle (comparative example 1) and a conventional polymer liquid retention additive (comparative example 2).
The applicant states that the present invention is illustrated by the above examples to the additive for battery and the preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. An additive for a battery, characterized in that the additive for a battery is a secondary particle formed of a primary particle of latex.
2. The additive for batteries according to claim 1, wherein the secondary particles have a particle diameter of 0.5 to 100.0 μm;
preferably, the specific surface area of the secondary particles is not less than 10m 2 /g；
Preferably, the swelling ratio of the secondary particles is 100% to 10000%.
3. The additive for a battery according to claim 1 or 2, wherein the latex primary particles comprise any one or a combination of at least two of styrene-acrylic latex particles, styrene-butadiene latex particles, pure acrylic latex particles, nitrile-butadiene latex particles, vinyl acetate-acrylic latex particles, silicone-acrylic latex particles, polyvinylidene fluoride latex particles, or polytetrafluoroethylene latex particles;
preferably, the latex primary particles have a particle size of 20 to 600nm.
4. A method for preparing the additive for batteries according to any one of claims 1 to 3, comprising: and spray-drying the polymer emulsion to form secondary particles to obtain the battery additive.
5. The method according to claim 4, wherein the polymer emulsion comprises any one or a combination of at least two of a styrene-acrylic emulsion, a styrene-butadiene emulsion, a pure acrylic emulsion, a nitrile-butadiene emulsion, a vinyl acetate-acrylic emulsion, a silicone-acrylic emulsion, a polyvinylidene fluoride emulsion, or a polytetrafluoroethylene emulsion;
preferably, the solids content of the polymer emulsion is from 30 to 80%.
6. The method of claim 4 or 5, wherein the inlet temperature of the spray-drying is 140-220 ℃;
preferably, the outlet temperature of the spray drying is 70-110 ℃;
preferably, the pressure of the spray drying is 0.2-0.8MPa;
preferably, the feeding speed of the polymer emulsion in the spray drying is 5-15mL/min.
7. An electrode material composition comprising the additive for batteries according to any one of claims 1 to 3.
8. The electrode material composition according to claim 7, characterized in that the electrode material composition comprises an electrode active material, a conductive agent, a binder, and the battery additive;
preferably, the battery additive is 0.01 to 1.00 parts by mass based on 100 parts by mass of the electrode active material.
9. A battery pole piece comprising a current collector and a coating disposed on the current collector, the material of the coating comprising the electrode material composition of claim 7 or 8.
10. An electrochemical energy storage device comprising at least one of the battery additive of any one of claims 1-3, the electrode material composition of claim 7 or 8, the battery pole piece of claim 9;
preferably, the electrochemical energy storage device comprises any one of a lithium ion battery, a sodium ion battery, a supercapacitor, a fuel cell or a solar cell.
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