CN113548817B - Preparation method, product and application of aerogel composite material - Google Patents
Preparation method, product and application of aerogel composite material Download PDFInfo
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Abstract
The invention provides a preparation method of aerogel composite material, a product and application thereof, and adopts an acid/alkali two-step catalysis method to prepare SiO 2 Sol, then directly mixing inorganic ceramic fiber with SiO 2 Sol compounding, fiber reinforced SiO prepared through sol-gel process 2 Aerogel composite material with SiO 2 The aerogel is taken as a main body, and the inorganic ceramic fibers are dispersed in an aerogel system to play a role in enhancing the aerogel system, so that the obtained structure has higher porosity, and is more beneficial to realizing the light weight of the battery and improving the retention amount of electrolyte; at the same time, the SiO of the present invention 2 The aerogel can also be filled in the gaps among the fibers and tightly wrapped on the surfaces of the fibers, so that better interface combination is formed between the aerogel and the fibers, and the mechanical property and the heat resistance of the composite material are improved. Thereby solving the problems of lithium ionThe problem of light weight of the battery, and simultaneously, the composite material has better mechanical property and heat resistance.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a preparation method, a product and application of an aerogel composite material.
Background
The lithium ion battery diaphragm is one of key components of the lithium ion battery, has important influence on the performance, safety and the like of the lithium ion battery, and along with the development of the lithium ion battery, particularly the high-speed development of the power lithium ion battery and the recent combustion events of some wearable devices and new energy automobiles, the lithium ion battery has higher requirements on the safety and the like of the lithium ion battery. The performance of the lithium ion battery separator, such as heat resistance, mechanical strength and the like, has important influence on the safety, the light weight and the like of the lithium ion battery.
Disclosure of Invention
One of the objects of the present invention is: the preparation method of the aerogel composite material is applied to the lithium ion battery diaphragm, solves the problem of light weight of the lithium ion battery, and simultaneously enables the composite material to have good mechanical property and heat resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method of preparing an aerogel composite comprising the steps of:
s1, preparing SiO by adopting an acid/alkali two-step catalysis method 2 Sol;
s2, mixing the inorganic ceramic fiber with the SiO obtained in the step S1 2 Sol compounding to obtain fiber composite SiO 2 A solution mixture;
s3, standing and aging for 18-36 h, putting into a constant temperature drying oven, and carrying out the step at 20-180 DEG CLadder-type heating treatment is carried out to obtain fiber reinforced SiO 2 Aerogel composites.
Preferably, in step S1, the acid/base two-step catalysis method is as follows: mixing and stirring tetraethoxysilane and ethanol, adding mixed solution of acid, water and ethanol for acid catalysis, adding alkali, water and ethanol for alkali catalysis after the tetraethoxysilane is fully hydrolyzed, and obtaining SiO 2 And (3) sol.
Preferably, the acid catalyzed pH is from 2.5 to 4; the pH of the base catalysis is 9-11.
Preferably, in step S2, the length of the inorganic ceramic fiber is 10 to 40mm.
Preferably, in step S2, the inorganic ceramic fiber is mixed with the SiO 2 The volume fraction ratio of the sol is 10: (10-100).
Preferably, in step S2, the inorganic ceramic fiber is Al 2 O 3 、SiO 2 、TiO 2 、Al(OH) 3 、MgO、Mg(OH) 2 、BrSO 4 、ZrO 2 Or one or more of montmorillonite.
Preferably, in step S3, the step-type temperature raising treatment conditions are as follows: step heating treatment is carried out at 60-180 ℃, and the temperature is kept for 1-3 h for each stop.
Preferably, the step-type heating treatment conditions are as follows: drying at 60deg.C, 80deg.C, 120deg.C and 180deg.C for 2 hr.
It is a second object of the present invention to provide an aerogel composite produced by the method for producing an aerogel composite as described in any of the above.
Another object of the present invention is to provide an aerogel composite slurry for a separator, comprising the aerogel composite material and an aqueous solvent.
Preferably, the aerogel composite has a particle size of less than or equal to 3 μm.
The fourth object of the present invention is to provide a separator, comprising a base film and a composite layer coating at least one surface of the base film, wherein the composite layer is obtained by coating the separator with aerogel composite slurry.
The fifth object of the present invention is to provide a lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet and a separator between the positive electrode sheet and the negative electrode sheet, wherein the separator is the separator.
Compared with the prior art, the invention has the beneficial effects that: the invention directly combines inorganic ceramic fiber and SiO 2 Sol compounding, fiber reinforced SiO prepared through sol-gel process 2 Aerogel composite material with SiO 2 The aerogel is taken as a main body, and the inorganic ceramic fibers are dispersed in an aerogel system to play a role in enhancing the aerogel system, so that the obtained structure has higher porosity, and is more beneficial to realizing the light weight of the battery and improving the retention amount of electrolyte; at the same time, the SiO of the present invention 2 The aerogel can also be filled in the gaps among the fibers and tightly wrapped on the surfaces of the fibers, so that better interface combination is formed between the aerogel and the fibers, and the mechanical property and the heat resistance of the composite material are improved. Therefore, the problem of light weight of the lithium ion battery is solved, and the composite material has good mechanical property and heat resistance.
Detailed Description
The first aspect of the present invention provides a method for preparing an aerogel composite, comprising the steps of:
s1, preparing SiO by adopting an acid/alkali two-step catalysis method 2 Sol;
s2, mixing the inorganic ceramic fiber with the SiO obtained in the step S1 2 Sol compounding to obtain fiber composite SiO 2 A solution mixture;
s3, standing and aging for 18-36 h, putting into a constant temperature drying oven, and performing stepped heating treatment at 20-180 ℃ to obtain fiber reinforced SiO 2 Aerogel composites.
Aerogel is a solid material with excellent heat insulation performance, has special microstructures such as high specific surface area, nano-scale holes, low density and the like, wherein the heat conductivity is 0.012mw/mk, and the density is 0.16mg/cm 3 Specific surface area of 400-1000 m 2 Per g, the porosity is 90-99.8%, and the internal volume is 99% of the gas groupThus, the least dense solids are currently known. Based on the characteristics of aerogel, the thermal performance is excellent, and the aerogel is applied to a lithium ion battery diaphragm coating material, so that the safety of a lithium ion battery is hopefully improved, and meanwhile, the lithium ion battery can be light.
The invention adopts an acid/alkali two-step catalysis method to prepare SiO 2 Aerogel and then combining the SiO 2 The aerogel is directly compounded with the inorganic ceramic fiber, and the aerogel is taken as a main body, so that the inorganic ceramic fiber is dispersed in an aerogel system to play a role in enhancing the aerogel system, and the obtained structure has higher porosity and is more beneficial to realizing the light weight of the battery and improving the retention amount of electrolyte; at the same time, the SiO of the present invention 2 The aerogel can also be filled in the gaps among the fibers and tightly wrapped on the surfaces of the fibers, so that better interface combination is formed between the aerogel and the fibers, and the mechanical property and the heat resistance of the composite material are improved. Therefore, the problem of light weight of the lithium ion battery is solved, and the composite material has good mechanical property and heat resistance.
Wherein, the aging time is prolonged to 18-36 h, so that the silicon-based raw material is fully hydrolyzed into silicon dioxide, the residual quantity of the silicon-based raw material is greatly reduced, and the inventor discovers that the aging time is prolonged, and then the stepped heating strengthening treatment is matched, so that the grid structure of the aerogel is more complete, and the fiber-reinforced SiO can be effectively improved 2 Interfacial strength of aerogel composites. Because of the effects of debonding, slipping, pulling out and the like between the aerogel and the fibers, the composite material has higher strength and toughness only when the interfacial binding force between the fibers and the aerogel is proper. This requires that the interface between the two should be strong enough to transmit axial loads and have high lateral strength on the one hand and weak enough to initiate lateral cracking along the interface to guide fiber pullout on the other hand.
Further, in step S1, the acid/base two-step catalysis method is as follows: mixing and stirring tetraethoxysilane and ethanol, adding mixed solution of acid, water and ethanol for acid catalysis, and adding alkali, water and ethanol for alkali catalysis after the tetraethoxysilane is fully hydrolyzedSiO is obtained 2 And (3) sol.
Further, the pH of the acid catalyst is 2.5-4; the pH of the base catalysis is 9-11. SiO produced at the acid/base temperature 2 The sol is compounded with inorganic ceramic fibers, so that the aerogel is more beneficial to establishing the function of taking the aerogel as a main body and taking the fibers as a reinforcing aerogel system.
Further, in step S2, the length of the inorganic ceramic fiber is 10 to 40mm.
Wherein the fiber-reinforced SiO 2 The toughening mechanism of aerogel composites mainly includes three aspects:
1) Crack propagation is hindered: when the fracture toughness of the fiber is larger than that of the matrix, cracks generated in the machine body are propagated to the fiber perpendicular to the interface, and the cracks can be blocked by the fiber;
2) And (3) fiber pulling: fibers with higher fracture toughness, when a crack of a matrix propagates to the fibers, the stress concentration causes interface dissociation between the fibers with weaker bonds and the matrix, and the fibers are broken at the weak points to consume external stress, so that the toughness of the material is increased;
3) Fiber bridging: after the matrix is cracked, the fibers are subjected to an applied load and bridge between the crack surfaces of the matrix, and the bridged fibers generate a force on the matrix which enables the cracks to merge, so that the toughness of the material is increased.
Thus, if too short inorganic ceramic fibers are adopted, the effects of fiber pulling and fiber bridging can be affected; if inorganic ceramic fiber with too long length is adopted, the inorganic ceramic fiber and SiO 2 The uniformity difficulty of aerogel matrix composite is greatly increased, and the strength of the composite material is also affected.
Further, in step S2, the inorganic ceramic fiber is mixed with the SiO 2 The volume fraction ratio of the sol is 10: (10-100). Further preferably, the inorganic ceramic fiber is bonded to the SiO 2 The volume fraction ratio of the sol is 10: (10-80). Still further preferably, the inorganic ceramic fiber is bonded to the SiO 2 The volume fraction ratio of the sol is 10: (20-60). Still more preferably, the inorganic ceramic fiber is bonded to the SiO 2 The volume fraction ratio of the sol is 10: (30-50). Inorganic ceramic fiber and SiO 2 The sol is compounded in a certain volume, so that the surface density of the coating can be obviously reduced, the porosity is improved, and the heat resistance of the material can be enhanced.
Further, in step S2, the inorganic ceramic fiber is Al 2 O 3 、SiO 2 、TiO 2 、Al(OH) 3 、MgO、Mg(OH) 2 、BrSO 4 、ZrO 2 Or one or more of montmorillonite.
Further, in step S3, the step-wise temperature-raising processing conditions are: step heating treatment is carried out at 60-180 ℃, and the temperature is kept for 1-3 h for each stop. Further, the step-type temperature-raising treatment conditions are as follows: drying at 60deg.C, 80deg.C, 120deg.C and 180deg.C for 2 hr. The inventor has proved by a large number of experiments that the reinforcement treatment is carried out under the stepped heating condition, so that the grid structure of the aerogel is more complete and the fiber reinforced SiO can be effectively improved 2 Interfacial strength of aerogel composites.
In a second aspect of the present invention, there is provided an aerogel composite produced by the method of producing an aerogel composite as described in any of the preceding claims.
In a third aspect of the present invention, there is provided an aerogel composite slurry for a separator, comprising the aerogel composite described above, an aqueous solvent, a dispersant, a thickener, a binder, and a wetting agent.
The aqueous solvent is adopted to be matched with the aerogel composite material with small particle size, so that the silicon-based raw material in the aerogel composite material can be continuously hydrolyzed and consumed, and the residual quantity of the silicon-based raw material is further reduced. Compared with the solvent replacement process adopted in the prior art, the preparation method omits the solvent replacement process, saves the use cost and recovery problem of the organic replacement agent, and can greatly reduce the residual quantity of the silicon-based raw material by prolonging the aging time, matching with proper stepped heating conditions and further consuming the water-based solvent in the application process, and the obtained aerogel grid structure is more complete due to the influence of the organic replacement agent.
Wherein the aqueous solvent includes, but is not limited to, pure water or deionized water. The dispersing agent comprises at least one of silicate, alkali metal phosphate and organic dispersing agent; the silicate is water glass, the alkali metal phosphate is at least one of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate, and the organic dispersing agent is at least one of triethylhexyl phosphate, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivative, polyacrylamide, guar gum and fatty acid polyethylene glycol ester. The thickener is at least one of hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose and methyl cellulose. Such binders include, but are not limited to, various aqueous binders such as acrylic. The wetting agent is at least one of anionic and nonionic surfactants such as dimethyl siloxane and N-methyl pyrrolidone.
Further, the aerogel composite has a particle size of less than or equal to 3 μm. Before preparing the aerogel composite slurry, the particle size of the aerogel composite material obtained by the method is crushed to be less than or equal to 3 mu m, so that the dispersion of the slurry and the thickness uniformity of a subsequent coating are facilitated.
The fourth object of the present invention is to provide a separator, comprising a base film and a composite layer coating at least one surface of the base film, wherein the composite layer is obtained by coating the separator with aerogel composite slurry.
The base film includes, but is not limited to, one or more combinations of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fibers, and the like.
The fifth object of the present invention is to provide a lithium ion battery, comprising a positive electrode sheet, a negative electrode sheet and a separator between the positive electrode sheet and the negative electrode sheet, wherein the separator is the separator.
Wherein the active material layer coated on the positive electrode sheet can be a material having a chemical formula such as Li a Ni x Co y M z O 2-b N b (wherein 0.95.ltoreq.a.ltoreq.1.2, x)>0, y is greater than or equal to 0, z is greater than or equal to 0, and x+y+z=1, 0 is greater than or equal to b is greater than or equal to 1, M is selected from a combination of one or more of Mn, al, N is selected from a combination of one or more of F, P, S), the positive electrode active material may also be a combination of one or more of compounds including but not limited to LiCoO 2 、LiNiO 2 、LiVO 2 、LiCrO 2 、LiMn 2 O 4 、LiCoMnO 4 、Li 2 NiMn 3 O 8 、LiNi 0.5 Mn 1.5 O 4 、LiCoPO 4 、LiMnPO 4 、LiFePO 4 、LiNiPO 4 、LiCoFSO 4 、CuS 2 、FeS 2 、MoS 2 、NiS、TiS 2 And the like. The positive electrode active material may be further subjected to a modification treatment, and a method of modifying the positive electrode active material should be known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, etc., and the material used for the modification treatment may be one or more combinations including but not limited to Al, B, P, zr, si, ti, ge, sn, mg, ce, W, etc. The positive current collector used for the positive plate is usually a structure or a part for collecting current, and the positive current collector may be various materials suitable for being used as a positive current collector of a lithium ion battery in the field, for example, the positive current collector may include, but is not limited to, a metal foil, etc., and more specifically may include, but is not limited to, an aluminum foil, etc.
The active material layer coated on the negative electrode sheet may be one or more of graphite, soft carbon, hard carbon, carbon fiber, mesophase carbon microsphere, silicon-based material, tin-based material, lithium titanate, or other metals capable of forming an alloy with lithium, etc. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon oxygen compound, silicon carbon compound and silicon alloy; the tin-based material can be selected from one or more of elemental tin, tin oxide and tin alloy. While the negative current collector used for the negative electrode sheet is generally a structure or a part for collecting current, the negative current collector may be various materials suitable for use as a negative current collector of a lithium ion battery in the field, for example, the negative current collector may be a metal foil, etc., and more specifically may include a copper foil, etc.
In order to make the technical solution and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A method of preparing an aerogel composite comprising the steps of:
s1, preparing SiO by adopting an acid/alkali two-step catalysis method 2 Sol: mixing Tetraethoxysilane (TEOS) with a certain amount of ethanol (EtOH) and stirring (V TEOS :V EtOH =1:4), and hydrochloric acid, 50vol% ethanol/water solution was added, and the pH was adjusted to the range of ph=2.5 to 4 for acid catalysis. After TEOS is fully hydrolyzed, ammonia water and 50vol% ethanol/water solution are added to adjust the pH value to be within the range of 9-11 for alkali catalysis, and finally SiO is obtained 2 And (3) sol.
S2, mixing the inorganic ceramic fiber with the SiO obtained in the step S1 2 Sol (V) Inorganic ceramic fiber ：V Sol-gel =1:5) to obtain fiber composite SiO 2 A solution mixture.
S3, standing and aging for 24 hours, so that the gel polycondensation reaction is continued, and the obtained gel grid structure is more complete; then placing into a constant temperature drying oven, and respectively drying at 60deg.C, 80deg.C, 120deg.C and 180deg.C for 2 hr to obtain fiber reinforced SiO 2 Aerogel composites.
An aerogel composite slurry for a diaphragm, comprising the aerogel composite material prepared by the above, an aqueous solvent, a dispersing agent, a thickening agent, a binder and a wetting agent, wherein the particle size of the aerogel composite material is crushed to be less than or equal to 3 mu m.
The preparation method of the slurry comprises the following steps: the preparation method comprises the following steps of: siO (SiO) 2 Aerogel composite: dispersing agent: and (3) a thickening agent: an adhesive: wetting agent: solvent = 25:0.6:16:4:0.4:54, siO was first deposited 2 Dispersing the aerogel composite material and the dispersing agent into deionized water, adding stirring equipment, heating to 25 ℃ and stirring for 90min at the revolution speed of 1000r/min and the revolution speed of 30r/min to obtain a mixture A; adding a thickener into the obtained mixture A, and continuously stirring for 20min at the rotation rate of 1000r/min and the revolution rate of 30r/min at the temperature of 25 ℃ to obtain a stable dispersion system B; adding the adhesive and the wetting agent with Tg more than 100 ℃ into the dispersion system B at intervals of 20min in sequence, and filtering to obtain SiO 2 Aerogel composite slurry.
The diaphragm comprises a base film and a composite layer coating at least one surface of the base film, wherein the composite layer is obtained by coating the aerogel composite slurry.
The preparation method of the diaphragm comprises the following steps: taking a single-layer PE/PP multi-element system microporous membrane with the thickness of 5 mu m and the porosity of 37% as a base membrane; coating SiO on the surface of the base film in a micro gravure coating mode 2 Forming a composite layer of 2 μm from the aerogel composite slurry; drying at 40deg.C for 0.5min to obtain SiO-containing material 2 A septum of aerogel composite.
In addition, the diaphragm also comprises a polymer bonding layer, and the SiO-containing material obtained by the method 2 At least one side of the diaphragm of the aerogel composite material is coated with the polymer bonding layer to obtain the SiO-containing composite material with bonding performance 2 A septum of aerogel composite.
A lithium ion battery comprises a positive plate, a negative plate and a diaphragm which is arranged between the positive plate and the negative plate, wherein the diaphragm is the diaphragm.
Example 2
Unlike example 1, step S1 in the method of preparing an aerogel composite.
S1, preparing SiO by adopting an acid/alkali two-step catalysis method 2 Sol: ethyl Orthosilicate (TEOS) is mixed with a certain amount of ethanol and stirred (V TEOS :V EtOH =1:4), and hydrochloric acid, 50vol% ethanol/water solution was added, and the pH was adjusted to the range of ph=2.5 to 4 for acid catalysis. After TEOS is fully hydrolyzed, ammonia water and 50vol% ethanol/water solution are added to regulate pBase catalysis is carried out in the range of H=7-8, and finally SiO is obtained 2 And (3) sol.
The remainder is the same as embodiment 1 and will not be described here again.
Example 3
The difference from example 1 is step S2 in the preparation method of the aerogel composite.
S2, mixing the inorganic ceramic fiber with the SiO obtained in the step S1 2 Sol (V) Inorganic ceramic fiber ：V Sol-gel =2:5) to obtain a fiber composite SiO 2 A solution mixture.
The remainder is the same as embodiment 1 and will not be described here again.
Example 4
The difference from example 1 is step S2 in the preparation method of the aerogel composite.
S2, mixing the inorganic ceramic fiber with the SiO obtained in the step S1 2 Sol (V) Inorganic ceramic fiber ：V Sol-gel =3:5) to obtain a fiber composite SiO 2 A solution mixture.
The remainder is the same as embodiment 1 and will not be described here again.
Example 5
The difference from example 1 is step S2 in the preparation method of the aerogel composite.
S2, mixing the inorganic ceramic fiber with the SiO obtained in the step S1 2 Sol (V) Inorganic ceramic fiber ：V Sol-gel =4:5) to obtain fiber composite SiO 2 A solution mixture.
The remainder is the same as embodiment 1 and will not be described here again.
Example 6
Unlike example 3, step S1 in the preparation method of the aerogel composite is performed.
S1, preparing SiO by adopting an acid/alkali two-step catalysis method 2 Sol: ethyl Orthosilicate (TEOS) is mixed with a certain amount of ethanol and stirred (V TEOS :V EtOH =1:4), and hydrochloric acid, 50vol% ethanol/water solution was added, and the pH was adjusted to the range of ph=2.5 to 4 for acid catalysis. After TEOS is fully hydrolyzed, ammonia water and 50vol% ethanol are addedAdjusting pH value of aqueous solution to 7-8 for base catalysis to obtain SiO 2 And (3) sol.
The remainder is the same as embodiment 3 and will not be described here again.
Example 7
Unlike example 1, step S3 in the preparation method of the aerogel composite is performed.
S3, standing and aging for 24 hours, so that the gel polycondensation reaction is continued, and the obtained gel grid structure is more complete; then placing into a constant temperature drying oven, and respectively drying at 40deg.C, 60deg.C, 80deg.C and 120deg.C for 2 hr to obtain fiber reinforced SiO 2 Aerogel composites.
The remainder is the same as embodiment 1 and will not be described here again.
Example 8
Unlike example 1, step S3 in the preparation method of the aerogel composite is performed.
S3, standing and aging for 24 hours, so that the gel polycondensation reaction is continued, and the obtained gel grid structure is more complete; then placing into a constant temperature drying oven, and respectively drying at 60deg.C, 80deg.C, 100deg.C, 120deg.C for 2 hr to obtain fiber reinforced SiO 2 Aerogel composites.
The remainder is the same as embodiment 1 and will not be described here again.
Example 9
Unlike example 1, step S3 in the preparation method of the aerogel composite is performed.
S3, standing and aging for 24 hours, so that the gel polycondensation reaction is continued, and the obtained gel grid structure is more complete; then placing the mixture into a constant temperature drying oven, and respectively drying at 60 ℃, 80 ℃ and 120 ℃ for 3 hours to obtain the fiber reinforced SiO 2 Aerogel composites.
The remainder is the same as embodiment 1 and will not be described here again.
Example 10
Unlike example 3, step S3 in the preparation method of the aerogel composite is performed.
S3, standing and aging for 24 hours, so that the gel polycondensation reaction is continued, and the obtained gel grid structure is more complete; then put into a constantDrying in a warm drying oven at 60deg.C, 80deg.C, 100deg.C and 120deg.C for 2 hr to obtain fiber reinforced SiO 2 Aerogel composites.
The remainder is the same as embodiment 3 and will not be described here again.
Example 11
Unlike example 3, step S3 in the preparation method of the aerogel composite is performed.
S3, standing and aging for 24 hours, so that the gel polycondensation reaction is continued, and the obtained gel grid structure is more complete; then placing the mixture into a constant temperature drying oven, and respectively drying at 60 ℃, 80 ℃ and 120 ℃ for 3 hours to obtain the fiber reinforced SiO 2 Aerogel composites.
The remainder is the same as embodiment 3 and will not be described here again.
Comparative example 1
A method for preparing a ceramic diaphragm, comprising the steps of:
1) Ceramic slurry: the preparation method comprises the following steps of: alumina ceramic: dispersing agent: and (3) a thickening agent: an adhesive: wetting agent: solvent = 25:0.6:16:4: dispersing alumina ceramic particles with the particle size D50 of 1 mu m and a dispersing agent into deionized water, adding stirring equipment, heating to 25 ℃ and stirring for 90min at the rotation speed of 1000r/min and the revolution speed of 30r/min until stirring uniformly to obtain a mixture A; adding a thickener into the obtained mixture A, and continuously stirring for 20min at the rotation rate of 1000r/min and the revolution rate of 30r/min at the temperature of 25 ℃ to obtain a stable dispersion system B; adding a bonding agent and a wetting agent with the Tg of between 30 ℃ into the dispersion system B at intervals of 20 minutes in sequence, and filtering to obtain ceramic slurry;
2) Coating: taking a single-layer PE/PP multi-element system microporous membrane with the thickness of 5 mu m and the porosity of 37% as a base membrane; coating ceramic slurry on the surface of the base film in a micro-gravure coating mode to form a 2 mu m ceramic coating; and then drying at 40 ℃ for 0.5min to prepare a heat-resistant ceramic diaphragm, and then coating at least one surface of the heat-resistant ceramic diaphragm with a polymer bonding coating to prepare the low-impedance heat-resistant lithium ion battery diaphragm with bonding performance.
The remainder is the same as embodiment 1 and will not be described here again.
Comparative example 2
A method of preparing an aerogel composite comprising the steps of:
s1, preparing SiO by adopting an acid/alkali two-step catalysis method 2 Sol: ethyl Orthosilicate (TEOS) is mixed with a certain amount of ethanol and stirred (V TEOS :V EtOH =1:4), and hydrochloric acid, 50vol% ethanol/water solution was added, and the pH was adjusted to the range of ph=2.5 to 4 for acid catalysis. After TEOS is fully hydrolyzed, ammonia water and 50vol% ethanol/water solution are added to adjust the pH value to be within the range of 9-11 for alkali catalysis, and finally SiO is obtained 2 And (3) sol.
S2, siO obtained in the step S1 is processed 2 Standing and aging the sol for 24 hours to enable the gel polycondensation reaction to continue; then placing into a constant temperature drying oven, and respectively drying at 60deg.C, 80deg.C, 120deg.C and 180deg.C for 2 hr to obtain fiber reinforced SiO 2 Aerogel composites.
The remainder is the same as embodiment 1 and will not be described here again.
The separators prepared in examples 1 to 11 and comparative examples 1 to 2 were subjected to a porosity, a liquid retention amount, and a heat shrinkage property test. The test results are shown in Table 1 below.
TABLE 1
As can be seen from the above test results, the SiO obtained by the preparation method of the present invention 2 Compared with the diaphragm prepared by the traditional ceramic material application, the aerogel composite material has smaller coating surface density, higher porosity, higher liquid retention and better heat resistance.
Furthermore, as can be seen from the comparison of examples 1 to 11 and comparative example 2, the prepared SiO was controlled simultaneously 2 Sol, siO 2 Proportion of sol to inorganic ceramic fiber and fiber composite SiO 2 The aging time and the strengthening temperature of the solution mixture can obtain the product with better toughness and heat resistanceDissimilar fiber reinforced SiO 2 Aerogel composite material, diaphragm and lithium ion battery that contain this composite material not only light-weighted better, and the liquid retention volume also can be better.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (7)
1. The aerogel composite slurry for the diaphragm is characterized by comprising an aqueous solvent and an aerogel composite material, and the preparation method of the aerogel composite material comprises the following steps:
s1, preparing SiO2 sol by adopting an acid/alkali two-step catalysis method, wherein the acid/alkali two-step catalysis method comprises the following steps: mixing and stirring tetraethoxysilane and ethanol, adding acid, water and ethanol mixed solution for acid catalysis, adding alkali, water and ethanol for alkali catalysis after the tetraethoxysilane is fully hydrolyzed to obtain SiO2 sol, wherein the pH value of the acid catalysis is 2.5-4; the pH of the base catalysis is 9-11;
s2, compounding the inorganic ceramic fiber with the SiO2 sol obtained in the step S1 to obtain a fiber composite SiO2 solution mixture;
s3, standing and aging for 18-36 h, placing the mixture into a constant temperature drying oven, performing step heating treatment at 60-180 ℃, and respectively performing heat preservation and drying at 60 ℃, 80 ℃, 120 ℃ and 180 ℃ for 2h to obtain the fiber reinforced SiO2 aerogel composite material;
the SiO2 aerogel is directly compounded with the inorganic ceramic fiber, and the aerogel is taken as a main body, so that the inorganic ceramic fiber is dispersed in an aerogel system; meanwhile, the SiO2 aerogel is filled in gaps among the fibers and tightly wraps the surfaces of the fibers, so that better interface combination is formed between the aerogel and the fibers, and further the mechanical property and the heat resistance of the composite material are improved.
2. The aerogel composite slurry for a separator according to claim 1, wherein in step S2, the length of the inorganic ceramic fiber is 10 to 40mm.
3. The aerogel composite slurry for a separator according to claim 1, wherein in step S2, a volume fraction ratio of the inorganic ceramic fiber to the SiO2 sol is 10: (10-100).
4. The aerogel composite slurry for a separator according to claim 1, 2 or 3, wherein in step S2, the inorganic ceramic fiber is one or more of Al2O3, siO2, tiO2, al (OH) 3, mgO, mg (OH) 2, brSO4, zrO2, or montmorillonite.
5. The aerogel composite slurry for a separator of claim 1, wherein the aerogel composite has a particle size of less than or equal to 3 μιη.
6. A separator comprising a base film and a composite layer coating at least one surface of the base film, wherein the composite layer is obtained by coating the separator according to claim 1 or 5 with an aerogel composite slurry.
7. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, and a separator interposed between the positive electrode sheet and the negative electrode sheet, wherein the separator is the separator of claim 6.
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