CN114122623A - A lithium ion battery separator, its preparation method and its application - Google Patents
A lithium ion battery separator, its preparation method and its application Download PDFInfo
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- CN114122623A CN114122623A CN202010897359.9A CN202010897359A CN114122623A CN 114122623 A CN114122623 A CN 114122623A CN 202010897359 A CN202010897359 A CN 202010897359A CN 114122623 A CN114122623 A CN 114122623A
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明提供一种锂离子电池隔膜、其制备方法及其应用。所述锂离子电池隔膜包括基膜、陶瓷层、粘结性功能层，其中，所述陶瓷层涂覆于所述基膜的一侧，所述粘结性功能层涂覆于所述基膜和所述陶瓷层的外侧；或者，所述陶瓷层涂覆于所述基膜的两侧，所述粘结性功能层涂覆于所述陶瓷层的外侧；所述粘结性功能层为包含聚合物树脂与陶瓷颗粒的混合涂层。本发明的锂离子电池隔膜，不仅具有高粘结性及高剥离强度，分切过程端面无毛刺，而且具有较高的热稳定性，有效提高了锂离子电池的安全性。
The invention provides a lithium ion battery separator, a preparation method and application thereof. The lithium ion battery separator includes a base film, a ceramic layer, and an adhesive functional layer, wherein the ceramic layer is coated on one side of the base film, and the adhesive functional layer is coated on the base film and the outer side of the ceramic layer; or, the ceramic layer is coated on both sides of the base film, and the adhesive functional layer is coated on the outer side of the ceramic layer; the adhesive functional layer is Hybrid coating comprising polymer resin and ceramic particles. The lithium ion battery separator of the invention not only has high adhesiveness and high peel strength, no burr on the end face during the slitting process, but also has high thermal stability, which effectively improves the safety of the lithium ion battery.
Description
Technical Field
The invention relates to the field of secondary battery diaphragms, in particular to a lithium ion battery diaphragm, a preparation method thereof and a lithium ion battery adopting the lithium ion battery diaphragm.
Background
In recent years, the annual output of lithium ion batteries of three end products is increased in a step manner. In 2016, the capacity of both consumer batteries and power batteries reaches 20GWH, wherein the percentage of the soft package batteries in the consumer batteries reaches 75%, and the percentage of the soft package batteries in the power batteries also reaches 9%. And (3) displaying data: in 2016 ~ 2020, the demand of consumer lithium batteries will support the smooth increase of laminate polymer battery, and the total amount of power battery is expected to continue to keep higher acceleration, and wherein laminate polymer power battery accounts for than will continuously increase. By 2020, pouch power cell demand is expected to reach 67 GWh.
Different from square, cylindrical and aluminum-shell batteries, the soft package battery adopts an aluminum-plastic packaging film as the outer shell of the battery, the thickness of the aluminum-plastic film is about 110 mu m or less, and the appearance is soft and easy to deform. When the battery is invalid, the battery expands, the aluminum plastic film bulges, and the shell breakage caused by the increase of the pressure in the battery can not be caused. In addition, the weight of the soft package battery is 40% lighter than that of a steel shell battery with the same capacity, the capacity of the soft package battery is 10-15% higher than that of the steel shell battery with the same specification, the internal resistance is small, and the design is flexible.
The soft package lithium ion battery has the defects that the shell is easy to deform, and potential safety hazards exist in the transportation and use processes. In the prior art, the diaphragm and the polar plate are heated and bonded together through the oily PVDF coating film, so that the stiffness of the battery cell is increased, and the safety of the soft package battery is improved. In addition, the distance between the oily PVDF membrane and the polar plate is reduced, the thickness of the battery core is reduced, and the capacity of the battery is increased under the condition of the same specification and size. And the PVDF coating film has large liquid absorption and retention capacity on electrolyte, and contributes to the cycle performance of the battery. Due to the special contribution of the oily PVDF to the soft package battery and the increase of the demand of the soft package battery diaphragm, the research and development and industrialization of the tightening layout of the oily PVDF coating diaphragm are carried out in diaphragm enterprises at home and abroad.
Although the PVDF functional layer is directly coated on the polyolefin base film, because the compatibility of the coating liquid and the base film is better, the peeling force between the coating layer of the finished film and the base film is larger, and poor cutting does not exist, the thermal stability of the diaphragm of the adhesive porous layer directly coated on the surface of the polyolefin base film is poorer. In order to improve the high-temperature stability of the separator and the safety of the battery, a ceramic layer is generally coated on one or both surfaces of a polyolefin-based film, and then an adhesive porous layer is coated thereon. At this time, because the compatibility of the ceramic layer and the coating liquid is poor, the peeling force between the adhesive functional layer of the finished film and the ceramic layer is small, burrs are formed on the end face in the cutting process, and the cutting of the product is poor.
Therefore, a battery separator having high peel strength, high adhesion, and excellent appearance is urgently required to solve the above-mentioned technical problems.
Disclosure of Invention
The invention aims to provide a lithium ion battery diaphragm which not only has high cohesiveness and high peel strength, has no burrs on the end surface in the slitting process, but also has higher thermal stability, and effectively improves the safety of a lithium ion battery.
The invention also aims to provide a preparation method of the lithium ion battery diaphragm, the lithium ion battery diaphragm prepared by the method has high cohesiveness, high peel strength and high thermal stability, and the method is feasible and can be used for continuous industrial production.
In order to achieve the above object, the present invention provides a lithium ion battery separator, comprising a base film, a ceramic layer, and an adhesive functional layer, wherein the ceramic layer is coated on one side of the base film, and the adhesive functional layer is coated on the outer sides of the base film and the ceramic layer; or the ceramic layer is coated on two sides of the base film, and the adhesive functional layer is coated on the outer side of the ceramic layer; the adhesive functional layer is a mixed coating comprising a polymer resin and ceramic particles. The ceramic particles can be used as a framework of the adhesive functional layer to provide a compressive supporting force in the hot-pressing process of the lithium ion battery separator.
Preferably, the polymer resin is PVDF resin, and comprises two copolymers of vinylidene fluoride and hexafluoropropylene with different copolymerization proportions. The two copolymers with different copolymerization proportions are matched, so that the adhesive force of the adhesive functional layer can be effectively improved, and the adhesive functional layer can be prevented from being dissolved due to excessive swelling of electrolyte.
Preferably, the ceramic particles are subjected to an oleophilic modification treatment. The ceramic particles are preferably aluminum oxide, and the ceramic particles subjected to oleophylic modification treatment can be uniformly dispersed in the oily slurry.
Preferably, the adhesive functional layer is obtained by coating adhesive functional layer slurry, wherein the adhesive functional layer slurry comprises an oily solvent, a polymer resin, ceramic particles, a pore-forming agent and a dispersing agent.
Preferably, the pore former includes a small molecule pore former and a large molecule pore former.
The invention also provides a preparation method of the lithium ion battery diaphragm, which comprises the following steps:
(1) coating a ceramic layer on one side or both sides of a base film;
(2) after the film layer material obtained in the step (1) is unreeled, coating two sides of the film layer material obtained in the step (1) with adhesive functional layer slurry; the adhesive functional layer slurry comprises an oily solvent, polymer resin, ceramic particles, a pore-forming agent and a dispersing agent;
(3) the film layer material obtained in the step (2) sequentially enters a primary coagulation bath system, a secondary coagulation bath system and a water washing system for treatment;
(4) and (4) sequentially feeding the film layer material treated in the step (3) into a drying system and a heat setting system for drying and setting, thus obtaining the lithium ion battery diaphragm.
Preferably, the oily solvent is dimethylacetamide.
Preferably, the polymer resin is PVDF resin, and comprises two copolymers of vinylidene fluoride and hexafluoropropylene with different copolymerization proportions; preferably, the mass ratio of the two copolymers is 2-10: 2-10. The two copolymers with different copolymerization proportions are matched, so that the adhesive force of the adhesive functional layer can be effectively improved, and the adhesive functional layer can be prevented from being dissolved due to excessive swelling of electrolyte.
Preferably, the pore former comprises a small molecule pore former and a large molecule pore former; preferably, the mass ratio of the small molecule pore-forming agent to the large molecule pore-forming agent is 2-10: 2-10. Pore-forming agents with different molecular weights are adopted for matching, so that a cohesive functional layer formed by combining finger-shaped pores and honeycomb-shaped pores can be obtained, the permeability of the cohesive functional layer is increased, and smooth passing of lithium ions is guaranteed.
Preferably, the ceramic particles are subjected to oleophilic modification treatment; preferably, the ceramic particles account for 2-15% by mass of the adhesive functional layer slurry. The ceramic particles can be used as a framework of the adhesive functional layer to provide a compressive supporting force in the hot-pressing process of the lithium ion battery separator.
Preferably, the preparation method of the adhesive functional layer slurry comprises the following steps:
step S1, adding a certain amount of the dispersant into a certain amount of the oily solvent, heating and stirring to completely dissolve the dispersant;
step S2, adding a certain amount of ceramic particles into the mixed solution obtained in the step S1, and stirring at a high speed to uniformly disperse the ceramic particles;
and step S3, adding a certain amount of the polymer resin and the pore-forming agent into the mixed solution obtained in the step S2, and fully stirring until the polymer resin and the pore-forming agent are completely dissolved to obtain the adhesive functional layer slurry.
The invention also provides a lithium ion battery, and the lithium ion battery comprises the lithium ion battery diaphragm.
Preferably, the lithium ion battery diaphragm is prepared by adopting the preparation method of the lithium ion battery diaphragm.
The mixed coating containing polymer resin and ceramic particles is adopted as a cohesive functional layer to be coated on two sides of the base film and/or the ceramic layer, so that the ceramic particles are used as a framework of the cohesive functional layer to provide a compression-resistant supporting force in the hot-pressing process of the lithium ion battery diaphragm; by mixing and adopting two copolymers of vinylidene fluoride and hexafluoropropylene with different copolymerization ratios, the adhesive force of the adhesive functional layer can be effectively improved, and the adhesive functional layer can be ensured not to be excessively swelled and dissolved by electrolyte; thirdly, the pore-forming agents with different molecular weights are matched to obtain the cohesive functional layer combining the finger-shaped pores and the honeycomb-shaped pores, the pore distribution is more uniform, the permeability of the cohesive functional layer is effectively increased, and the smooth passing of lithium ions is ensured; fourthly, the dispersant is added into the slurry of the adhesive functional layer, so that on one hand, the dispersant can be used for eliminating partial static electricity, on the other hand, the dispersant can be used as a surfactant, one end of the dispersant is connected with the ceramic layer, and the other end of the dispersant is connected with the adhesive functional layer, so that the peeling force between the adhesive functional layer and the ceramic layer is effectively increased, and the slitting end face is improved.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
Fig. 1 is a Scanning Electron Microscope (SEM) image of an adhesive functional layer of example 1 of the present invention and comparative example 3.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". 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.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
One embodiment of the invention provides a lithium ion battery diaphragm, which comprises a base film, a ceramic layer and an adhesive functional layer, wherein the ceramic layer is coated on one side of the base film, and the adhesive functional layer is coated on the outer sides of the base film and the ceramic layer; the adhesive functional layer is a mixed coating comprising a polymer resin and ceramic particles.
As a preferred embodiment, the ceramic layer is coated on both sides of the base film, and the adhesive functional layer is coated on the outer side of the ceramic layer; the adhesive functional layer is a hybrid coating comprising a polymer resin and ceramic particles.
According to the invention, the surface of the base film is coated with the ceramic layer on one side or two sides, and the adhesive functional layer is used as the outermost layer of the lithium ion battery diaphragm, so that the thermal stability of the lithium ion battery diaphragm is effectively improved, wherein the adhesive functional layer adopts a mixed coating containing polymer resin and ceramic particles, and the ceramic particles can be used as a framework of the adhesive functional layer to provide a compression-resistant supporting force in the hot-pressing process of the lithium ion battery diaphragm.
The lithium ion battery diaphragm of the invention adopts the conventional base film and ceramic layer in the prior art, and the details are not repeated. Wherein the base film is preferably an ultra-high molecular weight polyethylene diaphragm having a thickness of 5 to 20 μm and a porosity of 35 to 50%. In addition, the thickness of the ceramic coating is preferably 1-5 μm on one side and 2-10 μm on two sides; the thickness of the adhesive functional layer is preferably 0.5-4 μm on one side and 1-8 μm on two sides, and the porosity is preferably 40-60%. The air permeability of the lithium ion battery diaphragm can reach 100-300S/100 cc.
In a preferred embodiment, the polymer resin in the adhesive functional layer is PVDF resin, and includes two copolymers of vinylidene fluoride and hexafluoropropylene having different copolymerization ratios. The two copolymers with different copolymerization proportions are matched, so that the adhesive force of the adhesive functional layer can be effectively improved, and the adhesive functional layer can be prevented from being excessively swelled and dissolved by electrolyte.
As a specific embodiment, the PVDF resin in the adhesive functional layer comprises a PVDF-A resin with a hexafluoropropylene copolymerization ratio of 0.5-5% and a PVDF-B resin with a hexafluoropropylene copolymerization ratio of 5-10%, and the mass ratio of the PVDF-A resin to the PVDF-B resin is 2-10: 2-10. The larger the copolymerization ratio of hexafluoropropylene is, the better the adhesiveness is, but the more easily the adhesive functional layer is swelled by the electrolyte, and meanwhile, the higher the probability of pore structure collapse is in the use process, so that the PVDF-A resin and the PVDF-B resin are mixed for use, on one hand, the problem of adhesion reduction caused by adding ceramic particles can be effectively improved, on the other hand, the pore structure can be effectively stabilized, and the adhesive functional layer is ensured to be not easily dissolved by excessive swelling of the electrolyte.
In a preferred embodiment, the ceramic particles in the adhesive functional layer are subjected to an oleophilic modification treatment. The ceramic particles are preferably aluminum oxide, and are preferably submicron ceramic alpha crystal; the ceramic particles after oleophylic modification treatment can be uniformly dispersed in the oily slurry.
As a preferred embodiment, the adhesive functional layer is obtained by coating an adhesive functional layer slurry including an oily solvent, a polymer resin, ceramic particles, a pore-forming agent, and a dispersant.
As a preferred embodiment, the pore former includes a small molecule pore former and a large molecule pore former. The pore-forming agents with different molecular weights are matched, so that the cohesive functional layer formed by combining the finger-shaped pores and the honeycomb-shaped pores can be obtained, the pore distribution is more uniform, the permeability of the cohesive functional layer is effectively increased, and the smooth passing of lithium ions is ensured.
The lithium ion battery diaphragm has the peeling strength between the adhesive functional layer and the ceramic layer larger than 30N/m, and the adhesive force between the adhesive functional layer and the polar plate larger than 15N/m.
Another embodiment of the present invention provides a method for preparing a lithium ion battery separator, including the steps of:
(1) coating a ceramic layer on one side or both sides of a base film;
(2) after the film layer material obtained in the step (1) is unreeled, coating two sides of the film layer material obtained in the step (1) with adhesive functional layer slurry; the adhesive functional layer slurry comprises an oily solvent, polymer resin, ceramic particles, a pore-forming agent and a dispersing agent;
(3) the film layer material obtained in the step (2) sequentially enters a primary coagulation bath system, a secondary coagulation bath system and a water washing system for treatment;
(4) the film layer material treated in the step (3) sequentially enters a drying system and a heat setting system for drying and setting, and the lithium ion battery diaphragm is obtained;
(5) and (4) rolling the lithium ion battery diaphragm obtained in the step (4).
Wherein, the base film and the ceramic layer in the step (1) are both made of the conventional base film material and the conventional ceramic layer material in the prior art, and the conventional ceramic layer coating process in the prior art is adopted, which is not described herein again.
In a preferable embodiment, in the step (2), the coating temperature of the adhesive functional layer slurry is 20-40 ℃, and the coating tension is less than or equal to 30N/m; if the coating temperature is lower than 20 ℃, the pore-forming agent is precipitated in the slurry in the coating process, and the delamination phenomenon is generated in the coating process; if the coating temperature is higher than 40 ℃, the problems of reduced slurry viscosity, thinner coating thickness and the like exist, and the performance of the adhesive functional layer is further influenced; if the coating tension is more than 30N/m, the diaphragm is seriously stretched, and the appearance defects such as rib holding and the like are easily generated after rolling.
As a preferable embodiment, in the step (2), the oily solvent in the adhesive functional layer slurry is Dimethylacetamide (DMAC), and the mass part of DMAC in the adhesive functional layer slurry is preferably 80% to 95%.
In step (2), the polymer resin in the slurry of the adhesive functional layer is a PVDF resin, and preferably includes two copolymers of vinylidene fluoride and hexafluoropropylene having different copolymerization ratios, and the mass ratio of the two copolymers is preferably 2-10: 2-10. The preferable copolymer of vinylidene fluoride and hexafluoropropylene with different copolymerization proportions is PVDF-A resin with hexafluoropropylene copolymerization proportion of 0.5-5% and PVDF-B resin with hexafluoropropylene copolymerization proportion of 5-10%, wherein the PVDF-A resin accounts for 2-10% of the mass of the adhesive functional layer slurry, and the PVDF-B resin accounts for 2-10% of the mass of the adhesive functional layer slurry. The larger the copolymerization ratio of hexafluoropropylene is, the better the adhesiveness is, but the more easily the adhesive functional layer is swelled by the electrolyte, and meanwhile, the higher the probability of pore structure collapse is in the use process, so that the PVDF-A resin and the PVDF-B resin are mixed for use, on one hand, the problem of adhesion reduction caused by adding ceramic particles can be effectively improved, on the other hand, the pore structure can be effectively stabilized, and the adhesive functional layer is ensured to be not easily dissolved by excessive swelling of the electrolyte.
As a preferred embodiment, in the step (2), in the adhesive functional layer slurry, the ceramic particles are subjected to oleophilic modification treatment, preferably, aluminum oxide (Al)2O3) The amount of the binder-based functional layer slurry is preferably 2 to 15% by mass. The ceramic particles subjected to oleophylic modification treatment can be uniformly dispersed in DMAC (dimethylacetamide), and no additional dispersing agent is needed; the ceramic particles are used as a framework of the adhesive functional layer and provide a supporting force for compression resistance in the lithium ion battery diaphragm hot-pressing process.
In step (2), in the adhesive functional layer slurry, the pore-forming agent includes a small-molecule pore-forming agent and a large-molecule pore-forming agent, and the mass ratio of the small-molecule pore-forming agent to the large-molecule pore-forming agent is preferably 2-10: 2-10. Among them, the small molecule pore-forming agent is preferably a pore-forming agent having a molecular weight of 2000 or less, such as: polyvinyl alcohol, polyethylene glycol (PEG 400-PEG 2000); the macromolecular pore former is preferably a pore former having a molecular weight greater than 20000, such as: polyvinyl pyrrolidone K30(PVPK30), hydroxymethyl cellulose, Polyacrylamide (PAM), Hydrolyzed Polyacrylamide (HPAM), and the like. The small molecular pore-forming agent and the molecular chain of the PVDF resin have small entanglement and are easy to elute by a coagulating bath in the liquid-liquid phase separation process so as to form finger-shaped pores, and the large molecular pore-forming agent and the molecular chain of the PVDF resin have more entanglement points and are eluted at a relatively low speed so as to form a honeycomb-shaped pore structure together with the small molecular pore-forming agent. In the invention, the mass part of the small molecular pore-forming agent in the adhesive functional layer slurry is preferably 2-10%, and the mass part of the large molecular pore-forming agent in the adhesive functional layer slurry is preferably 2-10%. The pore-forming agents with different molecular weights are matched, so that the cohesive functional layer formed by combining the finger-shaped pores and the honeycomb-shaped pores can be obtained, the pore distribution is more uniform, the permeability of the cohesive functional layer is effectively increased, and the smooth passing of lithium ions is ensured.
As a preferred embodiment, in the step (2), in the slurry for the adhesive functional layer, the dispersant is an oily dispersant, such as: triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, fatty acid polyglycol esters, etc., preferably unsaturated polyesters of primary form. Different from the traditional coupling agent or surfactant, the dispersant disclosed by the invention can be uniformly dissolved in DMAC (dimethylacetamide) firstly, cannot cause caking and reaction on slurry, and cannot be eluted in the coagulating bath and water washing processes. In the invention, the dispersant accounts for 0.1-3% of the adhesive functional layer slurry by mass preferably. The dispersing agent can be used for eliminating partial static electricity on one hand, and on the other hand, the dispersing agent can be used as a surfactant, one end of the dispersing agent is connected with the ceramic layer, and the other end of the dispersing agent is connected with the adhesive functional layer, so that the peeling force between the adhesive functional layer and the ceramic layer is effectively increased, and the slitting end face is improved.
As a preferred embodiment, in the step (2), the method for preparing the adhesive functional layer slurry includes:
step S1, adding a certain amount of dispersant into a certain amount of oily solvent, heating and stirring to completely dissolve the dispersant;
step S2, adding a certain amount of ceramic particles into the mixed solution obtained in the step S1, and stirring at a high speed to uniformly disperse the ceramic particles;
and step S3, adding a certain amount of polymer resin and pore-forming agent into the mixed solution obtained in the step S2, and fully stirring until the polymer resin and the pore-forming agent are completely dissolved to obtain the adhesive functional layer slurry.
In a preferred embodiment, in the preparation method of the adhesive functional layer slurry, in step S1, a dispersant is added to DMAC, and the mixture is heated to 20 to 40 ℃ and stirred at a low speed (100 r/min or less) until the dispersant is completely dissolved. In the invention, the dispersing agent is firstly added into DMAC, and the adding amount is small; if the dispersing agent is added in the later period, the condition of uneven dispersion is caused by the high viscosity of the whole material.
In a preferred embodiment, in the preparation method of the adhesive functional layer slurry, in step S2, the ceramic particles after the lipophilic modification treatment are added to the mixed solution obtained in step S1, and the mixture is stirred at a high speed (not less than 500r/min) for 0.5 to 1 hour until the ceramic particles are uniformly dispersed.
In the invention, the dispersing agent is firstly added into DMAC, and the adding amount is small; the PVDF resin is added in the last step, so that the condition that the dispersing agent, the ceramic particles and the like are not uniformly dispersed due to high viscosity of the slurry is effectively avoided.
In a preferred embodiment, in the step (3), the film material obtained in the step (2) enters a primary coagulation bath system to be subjected to phase separation. In this process, the DMAC in the coating is double diffused with the DMAC in the primary coagulation bath system, and the DMAC concentration in the primary coagulation bath is the kinetics of the double diffusion. In the primary coagulation bath system, the mass part of the DMAC is preferably 60-90%. By adopting a high-concentration plasticizing bath system (namely a primary coagulation bath system), the liquid-liquid phase separation time is delayed, the phase separation speed is controlled, the pore diameter is adjusted, and the coating with the macroporous structure is prepared, so that the coating is prevented from deforming and blocking pores under stress. And if the concentration of the DMAC in the primary coagulation bath is too low, the DMAC diffusion process is accelerated, the phase separation time of the DMAC and the PVDF resin in the coating is short, the pore diameter is small, a skin layer is easy to form, and the preparation of surface pores is not facilitated. After the primary coagulation bath, the DMAC content of the coating is reduced, the PVDF of the surface layer is solidified, but the core still needs to be subjected to continuous phase separation, so that a secondary coagulation bath is needed. In the secondary coagulation bath system, the mass part of DMAC is preferably 30-50%. And finally, entering a water washing system, wherein the mass part of DMAC in the water washing system is less than or equal to 3%. The water washing is helpful for fully cleaning the residual DMAC on the film material, and a large amount of organic waste gas is avoided in the subsequent drying process.
As a preferred embodiment, in the step (4), the drying system adopts 2 modes of air drying and roller drying, wherein the air temperature is preferably 50-80 ℃, the roller temperature is preferably 40-60 ℃, and the roller surface temperature is not too high, so that the membrane is prevented from being scalded; the heat setting system adopts a carrier roller and an air drying mode, wherein the air temperature is preferably 80-120 ℃.
In a preferred embodiment, in the step (5), the tension in the winding process is controlled to be less than or equal to 5N/m. In addition, in the step (5), before the winding system is used for winding, a performance testing step may be added, for example, an online thickness measuring system is used for measuring the thickness of the lithium ion battery diaphragm, and/or a defect detecting system is used for detecting whether a defect exists in the lithium ion battery diaphragm, and the like.
Another embodiment of the present invention also provides a lithium ion battery comprising the lithium ion battery separator of the present invention.
As a preferred embodiment, the separator in the lithium ion battery is prepared by the preparation method of the lithium ion battery separator of the present invention.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
In this embodiment, the lithium ion battery diaphragm includes base film, ceramic layer, cohesiveness functional layer, and wherein, the ceramic layer coats in the both sides of base film, and the cohesiveness functional layer coats in the outside of ceramic layer, as the outermost layer of lithium ion battery diaphragm. The adhesive functional layer is a mixed coating containing polymer resin and ceramic particles, wherein the polymer resin is PVDF resin, and comprises PVDF-A resin with the copolymerization proportion of hexafluoropropylene of 0.5-5% and PVDF-B resin with the copolymerization proportion of hexafluoropropylene of 5-10%, and the mass ratio of the PVDF-A resin to the PVDF-B resin is 4: 1; the ceramic particles are alpha-Al2O3It is subjected to oleophylic modification treatment; alpha-Al2O3And the mass ratio of the PVDF-A resin to the PVDF-B resin is 4:4: 1.
Through performance tests, the lithium ion battery diaphragm of the embodiment has the thickness of 16.1 mu m and the mask density of 12 +/-1.5 g/m2The air permeability value is 200 +/-30S/100 cc. Wherein, the adhesive functional layer shows uniformly distributed finger-shaped holes and honeycomb-shaped holes combination as shown in fig. 1(a) by observation of a scanning electron microscope.
The lithium ion battery of the embodiment comprises the lithium ion battery diaphragm.
The preparation method of the lithium ion battery separator of the embodiment comprises the following steps: placing a base film with a ceramic layer coated on both sidesAfter rolling, a micro-concave roller is adopted to coat the adhesive functional layer on the two sides at the same time, the temperature of the coating slurry is 30 ℃, and the coating tension is less than or equal to 30N/m. Wherein, the adhesive functional layer slurry comprises the following components: 82% of Dimethylacetamide (DMAC), 4% of PVDF-A resin with 0.5% -5% of hexafluoropropylene copolymerization ratio, 1% of PVDF-B resin with 5% -10% of hexafluoropropylene copolymerization ratio, and alpha-Al2O34% by mass, 6% by mass of the small molecular pore-forming agent PEG2000, 2% by mass of the large molecular pore-forming agent PVPK30 and 1% by mass of the unsaturated polyester in the primary shape of the dispersing agent; the preparation method comprises the following steps: step S1, adding 1 mass percent of unsaturated polyester in the primary shape of the dispersant into 82 mass percent of DMAC, heating to 30 ℃, and stirring at a low speed (less than or equal to 100r/min) to completely dissolve the dispersant; step S2, adding 4% by mass of alpha-Al2O3Adding the mixture into the obtained mixed solution, and stirring at a high speed (more than or equal to 500r/min) for 0.5 hour to uniformly disperse the ceramic particles; and step S3, adding 4% by mass of PVDF-A resin, 1% by mass of PVDF-B resin, 6% by mass of PEG2000 and 2% by mass of PVPK30 into the mixed solution obtained in the step S2, and fully stirring until the mixed solution is completely dissolved to obtain the composite material. The coated film material enters a primary coagulation bath system for phase splitting, wherein the primary coagulation bath is a mixed solution of DMAC (dimethylacetamide) and water, the mass concentration of DMAC is 70%, and the temperature of the primary coagulation bath is 35 ℃; then, the mixture enters a second-stage coagulation bath, the components of the mixture are the same as those of the first-stage coagulation bath, the mixture is also a mixed solution of DMAC (dimethylacetamide) and water, the mass concentration of DMAC is 40%, and the temperature of the second-stage coagulation bath is 35 ℃; and then entering a water washing system, wherein the components are still a mixed solution of DMAC and water, and the mass concentration of the DMAC is 3%. The temperature of the water washing system is controlled to be 30 ℃, and all the coagulating baths and the water washing system are equipped with ultrasound. Then the film material sequentially passes through a drying system and a heat setting system, wherein the air temperature in the drying system is 70 ℃, and the roller temperature is 50 ℃; the air temperature in the heat setting system is 100 ℃. Drying and heat setting to obtain the lithium ion battery diaphragm, and rolling by a rolling system.
Example 2
In this embodiment, the lithium ion battery separator includes a base film, a ceramic layer, and an adhesive functional layer, wherein the ceramic layer is made of a ceramic materialThe ceramic layer is coated on one side of the base film, and the adhesive functional layer is coated on the outer sides of the base film and the ceramic layer and serves as the outermost layer of the lithium ion battery diaphragm. The adhesive functional layer is a mixed coating containing polymer resin and ceramic particles, wherein the polymer resin is PVDF resin, and comprises PVDF-A resin with the copolymerization proportion of hexafluoropropylene of 0.5-5% and PVDF-B resin with the copolymerization proportion of hexafluoropropylene of 5-10%, and the mass ratio of the PVDF-A resin to the PVDF-B resin is 1: 4; the ceramic particles are alpha-Al2O3It is subjected to oleophylic modification treatment; alpha-Al2O3And the mass ratio of the PVDF-A resin to the PVDF-B resin is 4:1: 4.
Through performance tests, the lithium ion battery diaphragm of the embodiment has the thickness of 15.5 mu m and the mask density of 11 +/-1.5 g/m2The air permeability value is 180 +/-30S/100 cc.
The lithium ion battery of the embodiment comprises the lithium ion battery diaphragm.
The preparation method of the lithium ion battery separator of the embodiment comprises the following steps: after the base film with the ceramic layer coated on the single surface is unreeled, a slightly concave roller is adopted to coat the adhesive functional layer on the double surfaces simultaneously, the coating slurry temperature is 20 ℃, and the coating tension is less than or equal to 30N/m. Wherein, the adhesive functional layer slurry comprises the following components: 78.9 percent of Dimethylacetamide (DMAC), 1 percent of PVDF-A resin with 0.5 to 5 percent of hexafluoropropylene copolymerization ratio, 4 percent of PVDF-B resin with 5 to 10 percent of hexafluoropropylene copolymerization ratio, and alpha-Al2O34% by mass, 10% by mass of the small molecular pore-forming agent PEG400, 2% by mass of the large molecular pore-forming agent HPAM and 0.1% by mass of the dispersing agent sodium dodecyl sulfate; the preparation method comprises the following steps: step S1, adding 0.1 mass percent of dispersant sodium dodecyl sulfate into 78.9 mass percent of DMAC, heating to 35 ℃, and stirring at a low speed (less than or equal to 100r/min) to completely dissolve the dispersant; step S2, adding 4% by mass of alpha-Al2O3Adding the mixture into the obtained mixed solution, and stirring at a high speed (more than or equal to 500r/min) for 1 hour to uniformly disperse the ceramic particles; step S3, adding 1% by mass of PVDF-A resin, 4% by mass of PVDF-B resin, 10% by mass of PEG400, and 2% by mass of HPAM to the mixed solution obtained in step S2, and fillingStirring until the components are completely dissolved, and obtaining the product. The coated film material enters a primary coagulation bath system for phase separation, wherein the primary coagulation bath is a mixed solution of DMAC (dimethylacetamide) and water, the mass concentration of DMAC is 70%, and the temperature of the primary coagulation bath is 30 ℃; then entering a second-stage coagulating bath, wherein the components of the second-stage coagulating bath are the same as those of the first-stage coagulating bath, the second-stage coagulating bath is also a mixed solution of DMAC and water, the mass concentration of DMAC is 30%, and the temperature of the second-stage coagulating bath is 30 ℃; and then entering a water washing system, wherein the components are still a mixed solution of DMAC and water, and the mass concentration of the DMAC is 2%. The temperature of the water washing system is controlled to be 25 ℃, and all the coagulating baths and the water washing system are equipped with ultrasound. Then the film material sequentially passes through a drying system and a heat setting system, wherein the air temperature in the drying system is 50 ℃, and the roller temperature is 60 ℃; the air temperature in the heat setting system is 120 ℃. Drying and heat setting to obtain the lithium ion battery diaphragm, and rolling by a rolling system.
Example 3
In this embodiment, the lithium ion battery diaphragm includes base film, ceramic layer, cohesiveness functional layer, and wherein, the ceramic layer coats in the both sides of base film, and the cohesiveness functional layer coats in the outside of ceramic layer, as the outermost layer of lithium ion battery diaphragm. The adhesive functional layer is a mixed coating containing polymer resin and ceramic particles, wherein the polymer resin is PVDF resin, and comprises PVDF-A resin with the copolymerization proportion of hexafluoropropylene of 0.5-5% and PVDF-B resin with the copolymerization proportion of hexafluoropropylene of 5-10%, and the mass ratio of the PVDF-A resin to the PVDF-B resin is 2: 1; the ceramic particles are alpha-Al2O3It is subjected to oleophylic modification treatment; alpha-Al2O3And the mass ratio of the PVDF-A resin to the PVDF-B resin is 1:2: 1.
Through performance tests, the thickness of the lithium ion battery diaphragm of the embodiment is 17 μm, and the density of the mask is 13 +/-1.5 g/m2The air permeability value is 250 +/-30S/100 cc.
The lithium ion battery of the embodiment comprises the lithium ion battery diaphragm.
The preparation method of the lithium ion battery separator of the embodiment comprises the following steps: after the base film with the ceramic layers coated on the two sides is unreeled, a slightly concave roller is adopted to coat the adhesive functional layers on the two sides simultaneously, the temperature of coating slurry is 40 ℃,the coating tension is less than or equal to 30N/m. Wherein, the adhesive functional layer slurry comprises the following components: 74 percent of Dimethylacetamide (DMAC), 6 percent of PVDF-A resin with 0.5 to 5 percent of hexafluoropropylene copolymerization ratio, 3 percent of PVDF-B resin with 5 to 10 percent of hexafluoropropylene copolymerization ratio, and alpha-Al2O33% of the mass, 5% of the mass of the small molecular pore-forming agent PEG1000, 8% of the mass of the large molecular pore-forming agent PVPK30 and 1% of the mass of the dispersant fatty acid polyglycol ester; the preparation method comprises the following steps: step S1, adding 1% by mass of dispersant fatty acid polyglycol ester into 74% by mass of DMAC, heating to 40 ℃, and stirring at a low speed (less than or equal to 100r/min) to completely dissolve the dispersant; step S2, adding 3% by mass of alpha-Al2O3Adding the mixture into the obtained mixed solution, and stirring at a high speed (more than or equal to 500r/min) for 1 hour to uniformly disperse the ceramic particles; and step S3, adding 6 mass percent of PVDF-A resin, 3 mass percent of PVDF-B resin, 5 mass percent of PEG1000 and 8 mass percent of PVPK30 into the mixed solution obtained in the step S2, and fully stirring until the PVDF-A resin, the PVDF-B resin, the PEG1000 and the PVPK30 are completely dissolved to obtain the composite material. The coated film material enters a primary coagulation bath system for phase splitting, wherein the primary coagulation bath is a mixed solution of DMAC (dimethylacetamide) and water, the mass concentration of DMAC is 75%, and the temperature of the primary coagulation bath is 40 ℃; then entering a second-stage coagulation bath, wherein the components of the second-stage coagulation bath are the same as those of the first-stage coagulation bath, the second-stage coagulation bath is also a mixed solution of DMAC and water, the mass concentration of DMAC is 50%, and the temperature of the second-stage coagulation bath is 40 ℃; and then entering a water washing system, wherein the components are still a mixed solution of DMAC and water, and the mass concentration of the DMAC is 1%. The temperature of the water washing system is controlled to be 35 ℃, and all the coagulating baths and the water washing system are equipped with ultrasound. Then the film material sequentially passes through a drying system and a heat setting system, wherein the air temperature in the drying system is 80 ℃, and the roller temperature is 40 ℃; the air temperature in the heat setting system is 95 ℃. Drying and heat setting to obtain the lithium ion battery diaphragm, and rolling by a rolling system.
Comparative example 1
The comparative example is different from example 1 only in that the slurry used to prepare the adhesive functional layer of the lithium ion battery separator in the comparative example does not contain PVDF-B resin.
Through performance testThe lithium ion battery diaphragm of the comparative example has the thickness of 15.9 mu m and the mask density of 12 +/-1.5 g/m2The air permeability value is 190 +/-30S/100 cc.
Comparative example 2
The comparative example is different from example 1 only in that the slurry used to prepare the adhesive functional layer of the lithium ion battery separator in the comparative example does not contain a dispersant.
Through performance tests, the lithium ion battery diaphragm of the comparative example has the thickness of 16.2 mu m and the mask density of 12 +/-1.5 g/m2The air permeability value is 195 +/-30S/100 cc.
Comparative example 3
The comparative example is different from example 1 only in that the slurry used to prepare the adhesive functional layer of the lithium ion battery separator in the comparative example does not contain a macromolecular pore-forming agent.
Through performance tests, the lithium ion battery diaphragm of the comparative example has the thickness of 16.2 mu m and the mask density of 12 +/-1.5 g/m2The air permeability value is 230 +/-30S/100 cc. Wherein the adhesive functional layer exhibits a single finger hole as observed by a scanning electron microscope, as shown in FIG. 1 (B).
Comparative example 4
The comparative example is different from example 1 only in that the slurry used to prepare the adhesive functional layer of the lithium ion battery separator in the comparative example does not contain ceramic particles.
Through performance tests, the lithium ion battery diaphragm of the comparative example has the thickness of 14 mu m and the mask density of 10 +/-1.5 g/m2The air permeability value is 200 +/-30S/100 cc.
The lithium ion battery separators according to examples 1 to 3 and comparative examples 1 to 3 of the present invention were tested for their peel force by the following method, in which,
the method for testing the peeling force between the adhesive functional layer and the polar plate comprises the following steps: the lithium ion battery diaphragms of examples 1 to 3 and comparative examples 1 to 4 were respectively prepared into soft-package lithium ion batteries for testing, wherein the battery capacity was 1Ah, the positive electrode material was of ternary lithium nickel cobalt manganese oxide 523 type, the negative electrode material was artificial graphite, the electrolyte was lithium hexafluorophosphate, and the battery cell was of a winding type. Dry pressure conditions: hot pressing at 1000kgf for 3 seconds at 85 ℃. Hot pressing conditions after liquid injection: 600kgf hot pressing for 2 minutes at 65 ℃. And respectively testing the peeling force between the adhesive functional layer and the polar plate after dry pressing and wet pressing. Peel force test conditions: cutting the disassembled polar plate (bonded with the diaphragm into sample strips with the width of 1cm and the length of 10 cm), and testing the peeling force and the tensile speed between the diaphragm and the polar plate by adopting a universal tensile testing machine: 100 mm/min;
method for testing the peel force between an adhesive functional layer and a ceramic layer: a 3M adhesive tape having a width of 1cm and a length of 10cm was adhered to an adhesive functional layer, the lithium ion battery separators of examples 1 to 3 and comparative examples 1 to 4 were respectively cut into sample strips having a width of 1cm and a length of 10cm along both side edges of the 3M adhesive tape, a peeling force between the 3M adhesive tape and the separator was measured using a universal tensile tester, the 3M adhesive tape adhered the adhesive functional layer, and thus the measured results show a peeling force between the adhesive functional layer and the ceramic layer, a tensile speed: 100 mm/min.
The test results are shown in Table 1. As can be seen from table 1, if the slurry of the adhesive functional layer includes a single PVDF resin, if the slurry does not include PVDF-B resin, the peeling force between the adhesive functional layer and the polar plate is significantly reduced, thereby causing the defects of gaps between the polar plates after the soft package lithium ion battery is hot-pressed, large internal resistance of the battery, insufficient hardness of the battery core, and the like; if the slurry of the adhesive functional layer does not contain a dispersing agent, the peeling force between the adhesive functional layer and the ceramic layer is obviously reduced, so that burrs are formed on the end face in the cutting process, and the product is poor in cutting; if the adhesive functional layer slurry contains a single pore-forming agent, if the adhesive functional layer slurry does not contain a macromolecular pore-forming agent, the pore distribution of the lithium ion battery diaphragm is not uniform, so that the ion transmission process is not uniform, and the polarization internal resistance is severe and the discharge capacity is low when the high-rate discharge is carried out; if the cohesive functional layer does not contain ceramic particles, the PVDF is a soft phase in the process of hot pressing of the battery core, particularly in the process of hot pressing after liquid injection, and the PVDF deforms under the action of temperature and pressure to cause the damage of a pore structure, so that the internal resistance of the battery is increased.
TABLE 1 basic physical property indexes of lithium ion battery separators of examples 1 to 3 and comparative examples 1 to 3
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A lithium ion battery diaphragm is characterized by comprising a base film, a ceramic layer and an adhesive functional layer, wherein,
the ceramic layer is coated on one side of the base film, and the adhesive functional layer is coated on the outer sides of the base film and the ceramic layer; or the ceramic layer is coated on two sides of the base film, and the adhesive functional layer is coated on the outer side of the ceramic layer;
the adhesive functional layer is a mixed coating comprising a polymer resin and ceramic particles.
2. The lithium ion battery separator according to claim 1, wherein the polymer resin is a PVDF resin comprising two copolymers of vinylidene fluoride and hexafluoropropylene with different copolymerization ratios.
3. The lithium ion battery separator according to claim 1, wherein the ceramic particles are subjected to oleophilic modification treatment.
4. The preparation method of the lithium ion battery separator is characterized by comprising the following steps:
(1) coating a ceramic layer on one side or both sides of a base film;
(2) after the film layer material obtained in the step (1) is unreeled, coating two sides of the film layer material obtained in the step (1) with adhesive functional layer slurry; the adhesive functional layer slurry comprises an oily solvent, polymer resin, ceramic particles, a pore-forming agent and a dispersing agent;
(3) the film layer material obtained in the step (2) sequentially enters a primary coagulation bath system, a secondary coagulation bath system and a water washing system for treatment;
(4) and (4) sequentially feeding the film layer material treated in the step (3) into a drying system and a heat setting system for drying and setting, thus obtaining the lithium ion battery diaphragm.
5. The method for preparing a lithium ion battery separator according to claim 4, wherein the oily solvent is dimethylacetamide.
6. The preparation method of the lithium ion battery separator according to claim 4 or 5, wherein the polymer resin is a PVDF resin, and comprises two copolymers of vinylidene fluoride and hexafluoropropylene with different copolymerization ratios;
preferably, the mass ratio of the two copolymers is 2-10: 2-10.
7. The method for preparing the lithium ion battery separator according to any one of claims 4 to 6, wherein the pore-forming agent comprises a small molecule pore-forming agent and a large molecule pore-forming agent;
preferably, the mass ratio of the small molecule pore-forming agent to the large molecule pore-forming agent is 2-10: 2-10.
8. The preparation method of the lithium ion battery separator according to any one of claims 4 to 7, wherein the ceramic particles are subjected to oleophilic modification treatment;
preferably, the ceramic particles account for 2-15% by mass of the adhesive functional layer slurry.
9. The method for producing a lithium ion battery separator according to any one of claims 4 to 8, wherein the method for producing the adhesive functional layer slurry comprises:
step S1, adding a certain amount of the dispersant into a certain amount of the oily solvent, heating and stirring to completely dissolve the dispersant;
step S2, adding a certain amount of ceramic particles into the mixed solution obtained in the step S1, and stirring at a high speed to uniformly disperse the ceramic particles;
and step S3, adding a certain amount of the polymer resin and the pore-forming agent into the mixed solution obtained in the step S2, and fully stirring until the polymer resin and the pore-forming agent are completely dissolved to obtain the adhesive functional layer slurry.
10. A lithium ion battery comprising the lithium ion battery separator according to any one of claims 1 to 3.
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| CN111518442A (en) * | 2020-03-23 | 2020-08-11 | 河北金力新能源科技股份有限公司 | Method for improving pore-forming of oil-based PVDF (polyvinylidene fluoride) of diaphragm coating |
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