CN101908645B - Ceramic/solid polymer electrolyte composite material with continuously and directionally-distributed wild phases and preparation method thereof - Google Patents
Ceramic/solid polymer electrolyte composite material with continuously and directionally-distributed wild phases and preparation method thereof Download PDFInfo
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- CN101908645B CN101908645B CN2010102408426A CN201010240842A CN101908645B CN 101908645 B CN101908645 B CN 101908645B CN 2010102408426 A CN2010102408426 A CN 2010102408426A CN 201010240842 A CN201010240842 A CN 201010240842A CN 101908645 B CN101908645 B CN 101908645B
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Abstract
The invention relates to a ceramic/solid polymer electrolyte composite material with continuously and directionally-distributed wild phases and a preparation method thereof, in particular to a ceramic/solid polymer electrolyte composite material and a preparation method thereof, which solve the problems of poor mechanical property and low conductivity caused by uneven distribution of ceramics in the conventional ceramic/solid polymer electrolyte composite material. The composite material consists of a solid polymer electrolyte and a solid phase. The preparation method comprises the following steps of: preparing slurry; injecting the slurry into a mould for freezing molding, freeze-drying and drying, and sintering to obtain a porous ceramic substrate; and permeating the liquid polymer electrolyte into the porous ceramic substrate under vacuum pressure, and curing at room temperature. In the composite material, the three-point flexural strength reaches between 100 and 150 MPa, fracture toughness reaches between 2.0 and 4.1 MPam<1/2>, and room temperature conductivity reaches between 10<-6> and 10<-4>S/cm. The ceramic/solid polymer electrolyte composite material has the advantages of simple preparation method and wide range of applicable material systems, and is applied to new energy systems, sensors and electrochemical devices.
Description
Technical field
The present invention relates to a kind of pottery/solid polymer electrolyte composite material and preparation method thereof.
Background technology
The continuous development of high-efficiency energy-storage-reforming unit has proposed new requirement to the performance of battery.Low cost, high reliability, persistence and environmental friendliness become the direction of novel battery development.Novel battery is for reducing greenhouse gas emission, and the flexibility that increases future source of energy is most important.What at present, research was more is the lithium battery that higher energy density and voltage can be provided.But because the liquid electrolyte in the lithium battery can cause adverse effect to environment, hindered the large-scale production of lithium battery, and adopted solid polymer electrolyte can effectively avoid the problems referred to above.Solid polymer electrolyte had both had the characteristics of the stability of polymer, had the liquid electrolyte conductive characteristic again, can effectively solve the problem of environmental pollution of lithium battery.But, the bad mechanical property of solid polymer electrolyte, the conductivity rate is low, and its application is restricted.In order to address this problem; Researchers join a certain amount of ceramic particle in the solid polymer electrolyte, make its mechanical performance and conductivity (the document 1:Solid State Ionics (solid ionic type surfactant) 1996 (85): 67-70) that is improved.And if ceramic phase is the continuous distribution state in solid polymer electrolyte; On the one hand its mechanical strength is greatly improved, on the other hand because the rigid-skeleton of continuous ceramic phase and the integrality of mechanical strength can make composite material be used as ionic conductance mutually.Make composite material have outstanding mechanical performance, high conductivity and good stable property (document 2:Journal of Power Sources (energy and raw material) 2009 (194): 66-72).
Summary of the invention
The objective of the invention is in order to solve ceramic skewness in existing pottery/solid polymer electrolyte composite material; The low problem of poor mechanical property, conductivity that causes pottery/solid polymer electrolyte composite material the invention provides pottery/solid polymer electrolyte composite material of a kind of wild phase continuously-directional distribution and preparation method thereof.
Pottery/solid polymer electrolyte composite material that wild phase continuously-directional of the present invention distributes by volume percentage is made up of 60% ~ 90% solid polymer electrolyte and 10% ~ 40% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain mass percent in the said solid polymer electrolyte and be 4% ~ 9% lithium salts; Said solid phase is made up of ceramic powder and sintering aid, and wherein the sintering aid quality accounts for 0% ~ 10% of solid phase gross mass, and sintering aid is MgO, CaO, BaO, Li
2O, TiO
2, AlN, Y
2O
3, Al
2O
3, La
2O
3, Yb
2O
3, Ce
2O
3, Nd
2O
3And SiO
2In a kind of or several kinds composition wherein.
The preparation method of pottery/solid polymer electrolyte composite material that wild phase continuously-directional of the present invention distributes realizes through following steps: one, ceramic powder, sintering aid, dispersant polyacrylic acid and deionized water are mixed; Ball milling 20 ~ 30h then; Obtain solid volume content and be 10% ~ 40% slurry; Wherein, solid phase is ceramic powder and sintering aid, and the quality of sintering aid accounts for 0% ~ 10% of solid phase gross mass; The polyacrylic quality of dispersant is 0.04% ~ 0.06% of a ceramic powder quality, and said sintering aid is MgO, CaO, BaO, Li
2O, TiO
2, AlN, Y
2O
3, Al
2O
3, La
2O
3, Yb
2O
3, Ce
2O
3, Nd
2O
3And SiO
2In a kind of or several kinds composition wherein; Two, the slurry that step 1 is obtained injects mould; After leaving standstill 10 ~ 30min; Condition bottom knockout being lower than 0 ℃ obtains the solid-state ceramic matrix, and wherein the base material of mould is a heat-conducting metal, and the heat-conducting metal of mould bottom is immersed in-200 ℃ ~-60 ℃ the refrigerant; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 24 ~ 72h, and then under 60 ~ 80 ℃ condition dry 1 ~ 2h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-20 ℃ ~-30 ℃; Four, with the porous ceramic matrices suitable base substrate at 1500 ~ 1800 ℃ of sintering 1 ~ 3h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; With seal of vessel, again container is evacuated to 0.1 ~ 1Pa then, under the pressure of 0.1 ~ 1Pa, keeps 8 ~ 15min then; Wherein contain mass percent in the liquid polymer electrolyte and be 4% ~ 9% lithium salts, keep that temperature is 70 ~ 180 ℃ in the container; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 10 ~ 20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
Below freezing point (0 ℃), carry out during the demoulding in the step 2 of the present invention, dissolve, influence the carrying out of subsequent step with the solid-state ceramic matrix that prevents moulding.When sintering aid is composition, mix with any ratio between each component in the step 1.
Ceramic phase continuously-directional as wild phase in pottery/solid polymer electrolyte composite material that wild phase continuously-directional of the present invention distributes distributes; Solid polymer electrolyte evenly is filled in the pottery of directional profile; Make the support humidification of ceramic phase bring into play better; Obtain the good pottery/solid polymer electrolyte composite material of mechanical property, three-point bending strength reaches 100 ~ 150MPa, and fracture toughness reaches 2.0 ~ 4.1MPam
1/2The ceramic phase continuously-directional distributes simultaneously, makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 10
-6~ 10
-4S/cm.
Ceramic phase is silicon nitride, aluminium oxide, silicon nitride, zirconia, hydroxyapatite or mullite in pottery/solid polymer electrolyte composite material of the present invention.Polymer dielectric is polyoxyethylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate or the Kynoar that is dissolved with lithium salts.Lithium salts is LiClO
4, LiBF4, LiAsF
6, LiPF6, LiCF
3SO
3, Li (CF
3SO
2)
2, or LiN (CF
3SO
2)
2
Preparation method's process conditions of pottery/solid polymer electrolyte composite material that wild phase continuously-directional of the present invention distributes are simple; Cost is low; The material system scope that is suitable for is wide, for the preparation of pottery/solid polymer electrolyte composite material provides a new way.At first utilize step 2 with the ceramic powder particle by the ice crystal in-situ solidifying, in solidification process, prolong the temperature gradient that mold bottom raises to the top formation temperature gradually; Then the water in the slurry prolongs temperature gradient direction oriented crystallization; Promptly simultaneously the ceramic powder grain orientation is solidified, make ceramic powder particle continuously-directional in the solid-state ceramic matrix distribute, the freeze drying through step 3 distils ice crystal then; Reburn the knot after obtain ceramic phase continuously-directional distributed porous ceramic matrix; Handle through the vacuum pressure infiltration method of step 5 again, polymer dielectric is filled in the porous ceramic matrices suitable, obtain pottery/solid polymer electrolyte composite material in cold curing.
The kind of kind and the refrigerant of the present invention through solid concentration, the ceramic powder of control ceramic size can obtain the composite material of different structure and performance.Whether sintering aid adds among the present invention, and those skilled in the art can judge according to the kind of routine operation and ceramic phase and obtain.
Pottery/solid polymer electrolyte composite material that wild phase continuously-directional of the present invention distributes can be applicable to lithium battery, new forms of energy system, transducer and electrochemical device.
Description of drawings
Fig. 1 is the structural representation of the mould that uses in the step 2 of embodiment 14; Fig. 2 is the structural representation that vacuum pressure oozes the equipment of employing in the step 5 of embodiment 14; Fig. 3 is the vertical section sem photograph of pottery/solid polymer electrolyte composite material of distributing of the wild phase continuously-directional of embodiment 46; Fig. 4 is the cross section sem photograph of pottery/solid polymer electrolyte composite material of distributing of the wild phase continuously-directional of embodiment 46.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 60% ~ 90% solid polymer electrolyte and 10% ~ 40% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain mass percent in the said solid polymer electrolyte and be 4% ~ 9% lithium salts; Said solid phase is made up of ceramic powder and sintering aid, and wherein the sintering aid quality accounts for 0% ~ 10% of solid phase gross mass, and sintering aid is MgO, CaO, BaO, Li
2O, TiO
2, AlN, Y
2O
3, Al
2O
3, La
2O
3, Yb
2O
3, Ce
2O
3, Nd
2O
3And SiO
2In a kind of or several kinds composition wherein.
According to those skilled in the art's routine operation and common practise, whether add sintering aid and can decide in the present embodiment according to the kind of ceramic powder.When sintering aid is composition, mix with any ratio between each component.
Ceramic phase continuously-directional as wild phase in pottery/solid polymer electrolyte composite material that the wild phase continuously-directional of this execution mode distributes distributes; Solid polymer electrolyte evenly is filled in the pottery of directional profile; Make the support humidification of ceramic phase bring into play better; Obtain the good pottery/solid polymer electrolyte composite material of mechanical property, three-point bending strength reaches 100 ~ 150MPa, and fracture toughness reaches 2.0 ~ 4.1MPam
1/2The ceramic phase continuously-directional distributes simultaneously, makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 10
-6~ 10
-4S/cm.
Embodiment two: this execution mode and embodiment one are different be pottery/solid polymer electrolyte composite material of distributing of wild phase continuously-directional by volume percentage form by 65% ~ 80% solid polymer electrolyte and 20% ~ 35% solid phase.Other parameter is identical with embodiment one.
Embodiment three: this execution mode and embodiment one are different be pottery/solid polymer electrolyte composite material of distributing of wild phase continuously-directional by volume percentage form by 70% solid polymer electrolyte and 30% solid phase.Other parameter is identical with embodiment one.
Embodiment four: this execution mode and embodiment one, two or three are different is that lithium salts in the solid polymer electrolyte is LiClO
4, LiBF
4, LiAsF
6, LiPF
6, LiCF
3SO
3, Li (CF
3SO
2)
2Perhaps LiN (CF
3SO
2)
2Other parameter is identical with embodiment one, two or three.
Lithium salts has good electric conductivity in the present embodiment.
Embodiment five: this execution mode is different with one of embodiment one to four is that polymer in the solid polymer electrolyte is polyoxyethylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate or Kynoar.Other parameter is identical with one of embodiment one to four.
Embodiment six: this execution mode is different with one of embodiment one to five is that to contain mass percent in the solid polymer electrolyte be 6% ~ 9% lithium salts.Other parameter is identical with one of embodiment one to five.
The conductivity of the mass percent of lithium salts and pottery/solid polymer electrolyte composite material is proportional in this execution mode, and the mass percent of occupying is big more, and conductivity is big more.
Embodiment seven: this execution mode is different with one of embodiment one to five is that to contain mass percent in the solid polymer electrolyte be 8% lithium salts.Other parameter is identical with one of embodiment one to five.
Embodiment eight: what this execution mode was different with one of embodiment one to seven is that ceramic powder is carborundum, silicon nitride, aluminium oxide, zirconia, hydroxyapatite or mullite.Other parameter is identical with one of embodiment one to seven.
Be not limited to above-mentioned concrete ceramic powder kind in this execution mode, other conventional ceramic powder of this area all can be used for this execution mode.
Embodiment nine: what this execution mode was different with one of embodiment one to eight is that said solid phase only is made up of ceramic powder, and said ceramic powder is aluminium oxide, zirconia, hydroxyapatite or mullite.Other parameter is identical with one of embodiment one to eight.
The ceramic powder that does not add sintering aid in this execution mode is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and not adding of can the judging ceramic powder that sintering aid can realize sintering is all applicable to this execution mode.
Embodiment ten: what this execution mode was different with one of embodiment one to eight is that said solid phase is made up of ceramic powder and sintering aid, and the sintering aid quality accounts for 1% ~ 10% of solid phase gross mass, and wherein ceramic powder is carborundum or silicon nitride.Other parameter is identical with one of embodiment one to eight.
The ceramic powder that needs in this execution mode to add sintering aid is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and the ceramic powder that in sintering process, needs to add sintering aid that can judge is all applicable to this execution mode.
Embodiment 11: what this execution mode was different with one of embodiment one to eight is that said solid phase is made up of ceramic powder and sintering aid, and the sintering aid quality accounts for 3% ~ 8% of solid phase gross mass, and wherein ceramic powder is carborundum or silicon nitride.Other parameter is identical with one of embodiment one to eight.
The ceramic powder that needs in this execution mode to add sintering aid is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and the ceramic powder that in sintering process, needs to add sintering aid that can judge is all applicable to this execution mode.
Embodiment 12: what this execution mode was different with one of embodiment one to eight is that said solid phase is made up of ceramic powder and sintering aid, and the sintering aid quality accounts for 6% of solid phase gross mass, and wherein ceramic powder is carborundum or silicon nitride.Other parameter is identical with one of embodiment one to eight.
The ceramic powder that needs in this execution mode to add sintering aid is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and the ceramic powder that in sintering process, needs to add sintering aid that can judge is all applicable to this execution mode.
Embodiment 13: what this execution mode was different with one of embodiment one to 12 is that sintering aid is MgO, Y
2O
3, Al
2O
3, AlN, TiO
2, La
2O
3, Yb
2O
3-La
2O
3, Yb
2O
3-Ce
2O
3, Yb
2O
3-MgO, Y
2O
3-La
2O
3, Y
2O
3-Ce
2O
3, Y
2O
3-MgO, Nd
2O
3-MgO, BaO-Al
2O
3-SiO
2, Y
2O
3-MgO-CaO, MgO-Al
2O
3-SiO
2Perhaps Li
2O-Al
2O
3-SiO
2Other parameter is identical with one of embodiment one to 12.
When this execution mode is composition when sintering aid, mix with any ratio between each component.
Embodiment 14: this execution mode is like the preparation method of the pottery/solid polymer electrolyte composite material of embodiment one described wild phase continuously-directional distribution; Realize through following steps: one, ceramic powder, sintering aid, dispersant polyacrylic acid and deionized water are mixed; Ball milling 20 ~ 30h then obtains solid volume content and is 10% ~ 40% slurry, wherein; Solid phase is ceramic powder and sintering aid; The quality of sintering aid accounts for 0% ~ 10% of solid phase gross mass, and the polyacrylic quality of dispersant is 0.04% ~ 0.06% of a ceramic powder quality, and said sintering aid is MgO, CaO, BaO, Li
2O, TiO
2, AlN, Y
2O
3, Al
2O
3, La
2O
3, Yb
2O
3, Ce
2O
3, Nd
2O
3And SiO
2In a kind of or several kinds composition wherein; Two, the slurry that step 1 is obtained injects mould; After leaving standstill 10 ~ 30min; Condition bottom knockout being lower than 0 ℃ obtains the solid-state ceramic matrix, and wherein the base material of mould is a heat-conducting metal, and the heat-conducting metal of mould bottom is immersed in-200 ℃ ~-60 ℃ the refrigerant; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 24 ~ 72h, and then under 60 ~ 80 ℃ condition dry 1 ~ 2h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-20 ℃ ~-30 ℃; Four, with the porous ceramic matrices suitable base substrate at 1500 ~ 1800 ℃ of sintering 1 ~ 3h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; With seal of vessel, again container is evacuated to 0.1 ~ 1Pa then, under the pressure of 0.1 ~ 1Pa, keeps 8 ~ 15min then; Wherein contain mass percent in the liquid polymer electrolyte and be 4% ~ 9% lithium salts, keep that temperature is 70 ~ 180 ℃ in the container; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 10 ~ 20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
Pottery/solid polymer electrolyte composite material that this execution mode obtains by volume percentage is made up of 60% ~ 90% solid polymer electrolyte and 10% ~ 40% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain mass percent in the said solid polymer electrolyte and be 4% ~ 9%% lithium salts; Said solid phase is made up of ceramic powder and sintering aid, and wherein the sintering aid quality accounts for 0% ~ 10% of solid phase gross mass.
When sintering aid is composition, mix with any ratio between each component in this execution mode step 1.
The structural representation of the mould that uses in this execution mode step 2 is as shown in Figure 1.A is for containing the container of coolant e among Fig. 1; D is the bottom of mould, is made up of conducting metal; C is the side of mould, is made up of nonmetallic materials; B is a slurry.Slurry is injected this mould; The temperature gradient that raises gradually in the direction formation temperature of prolonging mold bottom to upper opening portion; Make the water in the slurry prolong temperature gradient direction oriented crystallization; Promptly simultaneously the ceramic powder grain orientation is solidified, make ceramic powder particle continuously-directional in the solid-state ceramic matrix distribute.
The structural representation of the equipment that the vacuum pressure infiltration method of this execution mode step 5 is adopted is as shown in Figure 2.As shown in Figure 2, vacuum pump g vacuumizes processing through vacuum lead a to container b, and vacuum valve f is arranged on the vacuum lead a; Through the temperature in the heating plate d control container b, to guarantee that polymer dielectric c is a liquid state, porous ceramic matrices suitable e is immersed among the polymer dielectric c.
Preparation method's process conditions of this execution mode are simple, and cost is low, and the material system scope that is suitable for is wide, for the preparation of pottery/solid polymer electrolyte composite material provides a new way.
Embodiment 15: that this execution mode and embodiment 14 are different is ball milling 24h in the step 1.Other step and parameter are identical with embodiment 14.
Embodiment 16: this execution mode is different with embodiment 14 or 15 is that to obtain solid volume content in the step 1 be 20% ~ 35% slurry.Other step and parameter are identical with embodiment 14 or 15.
Embodiment 17: this execution mode is different with embodiment 14 or 15 is that to obtain solid volume content in the step 1 be 30% slurry.Other step and parameter are identical with embodiment 14 or 15.
Embodiment 18: what this execution mode was different with one of embodiment 14 to 17 is that ceramic powder is carborundum, silicon nitride, aluminium oxide, zirconia, hydroxyapatite or mullite in the step 1.Other step and parameter are identical with one of embodiment 14 to 17.
Be not limited to above-mentioned concrete ceramic powder kind in this execution mode, other conventional ceramic powder of this area all can be used for this execution mode.
Embodiment 19: what this execution mode was different with one of embodiment 14 to 18 is that solid phase only is made up of ceramic powder in the step 1, and said ceramic powder is aluminium oxide, zirconia, hydroxyapatite or mullite.Other step and parameter are identical with one of embodiment 14 to 18.
The ceramic powder that does not add sintering aid in this execution mode is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and not adding of can the judging ceramic powder that sintering aid can realize sintering is all applicable to this execution mode.
Embodiment 20: what this execution mode was different with one of embodiment 14 to 18 is that solid phase is made up of ceramic powder and sintering aid in the step 1; The sintering aid quality accounts for 1% ~ 10% of solid phase gross mass, and wherein ceramic powder is carborundum or silicon nitride.Other step and parameter are identical with one of embodiment 14 to 18.
The ceramic powder that needs in this execution mode to add sintering aid is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and the ceramic powder that in sintering process, needs to add sintering aid that can judge is all applicable to this execution mode.
Embodiment 21: what this execution mode was different with one of embodiment 14 to 18 is that solid phase is made up of ceramic powder and sintering aid in the step 1; The sintering aid quality accounts for 3% ~ 8% of solid phase gross mass, and wherein ceramic powder is carborundum or silicon nitride.Other step and parameter are identical with one of embodiment 14 to 18.
The ceramic powder that needs in this execution mode to add sintering aid is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and the ceramic powder that in sintering process, needs to add sintering aid that can judge is all applicable to this execution mode.
Embodiment 22: what this execution mode was different with one of embodiment 14 to 18 is that solid phase is made up of ceramic powder and sintering aid in the step 1; The sintering aid quality accounts for 6% of solid phase gross mass, and wherein ceramic powder is carborundum or silicon nitride.Other step and parameter are identical with one of embodiment 14 to 18.
The ceramic powder that needs in this execution mode to add sintering aid is not limited to above-mentioned several kinds, and those skilled in the art are according to general knowledge known in this field, and the ceramic powder that in sintering process, needs to add sintering aid that can judge is all applicable to this execution mode.
Embodiment 23: what this execution mode was different with one of embodiment 14 to 22 is that sintering aid is MgO, Y in the step 1
2O
3, Al
2O
3, AlN, TiO
2, La
2O
3, Yb
2O
3-La
2O
3, Yb
2O
3-Ce
2O
3, Yb
2O
3-MgO, Y
2O
3-La
2O
3, Y
2O
3-Ce
2O
3, Y
2O
3-MgO, Nd
2O
3-MgO, BaO-Al
2O
3-SiO
2, Y
2O
3-MgO-CaO, MgO-Al
2O
3-SiO
2Perhaps Li
2O-Al
2O
3-SiO
2Other step and parameter are identical with one of embodiment 14 to 22.
When this execution mode is composition when sintering aid, mix with any ratio between each component.
Embodiment 24: what this execution mode was different with one of embodiment 14 to 23 is that the slurry that in the step 2 step 1 is obtained injects mould, leaves standstill 20min.Other step and parameter are identical with one of embodiment 14 to 23.
Embodiment 25: what this execution mode was different with one of embodiment 14 to 24 is that the condition bottom knockout at-10 ℃ ~-2 ℃ obtains the solid-state ceramic matrix in the step 2.Other step and parameter are identical with one of embodiment 14 to 24.
The calcining temperature of this execution mode is enough to prevent that the solid-state ceramic matrix of moulding from dissolving, and does not influence the carrying out of subsequent step.
Embodiment 26: this execution mode is different with one of embodiment 14 to 25 is that refrigerant is a kind of in liquid nitrogen, liquid helium, alcohol, glycerine solvent or the ethylene glycol solvent or several kinds mixture wherein in the step 2.Other step and parameter are identical with one of embodiment 14 to 25.
When refrigerant is mixture, mix in this execution mode with the arbitrary volume ratio.
Embodiment 27: what this execution mode was different with one of embodiment 14 to 26 is that the solid-state ceramic matrix that in the step 3 step 2 is obtained is put into freeze dryer freeze drying 36 ~ 60h.Other step and parameter are identical with one of embodiment 14 to 26.
Embodiment 28: what this execution mode was different with one of embodiment 14 to 26 is that the solid-state ceramic matrix that in the step 3 step 2 is obtained is put into freeze dryer freeze drying 48h.Other step and parameter are identical with one of embodiment 14 to 26.
Embodiment 29: what this execution mode was different with one of embodiment 14 to 28 is that the freeze drying temperature is-22 ℃ ~-28 ℃ in the step 3.Other step and parameter are identical with one of embodiment 14 to 28.
Embodiment 30: what this execution mode was different with one of embodiment 14 to 28 is that the freeze drying temperature is-25 ℃ in the step 3.Other step and parameter are identical with one of embodiment 14 to 28.
Embodiment 31: this execution mode is different with one of embodiment 14 to 30 be in the step 4 with the porous ceramic matrices suitable base substrate at 1600 ~ 1800 ℃ of sintering 1.5 ~ 2.5h.Other step and parameter are identical with one of embodiment 14 to 30.
Embodiment 32: this execution mode is different with one of embodiment 14 to 30 be in the step 4 with the porous ceramic matrices suitable base substrate at 1700 ℃ of sintering 2h.Other step and parameter are identical with one of embodiment 14 to 30.
Embodiment 33: what this execution mode was different with one of embodiment 14 to 32 is that step 5 is evacuated to 0.3 ~ 0.8Pa with container again, under the pressure of 0.3 ~ 0.8Pa, keeps 10 ~ 14min then.Other step and parameter are identical with one of embodiment 14 to 32.
Embodiment 34: what this execution mode was different with one of embodiment 14 to 32 is that step 5 is evacuated to 0.6Pa with container again, under the pressure of 0.6Pa, keeps 12min then.Other step and parameter are identical with one of embodiment 14 to 32.
Embodiment 35: this execution mode is different with one of embodiment 14 to 34 is that to contain mass percent in the step 5 in the liquid polymer electrolyte be 6% ~ 9% lithium salts.Other step and parameter are identical with one of embodiment 14 to 34.
Embodiment 36: this execution mode is different with one of embodiment 14 to 34 is that to contain mass percent in the step 5 in the liquid polymer electrolyte be 8% lithium salts.Other step and parameter are identical with one of embodiment 14 to 34.
Embodiment 37: what this execution mode was different with one of embodiment 14 to 36 is that the lithium salts in the liquid polymer electrolyte is LiClO in the step 5
4, LiBF
4, LiAsF
6, LiPF
6, LiCF
3SO
3, Li (CF
3SO
2)
2Perhaps LiN (CF
3SO
2)
2Other step and parameter are identical with one of embodiment 14 to 36.
Lithium salts has good electric conductivity in the present embodiment.
Embodiment 38: what this execution mode was different with one of embodiment 14 to 37 is that the polymer in the liquid polymer electrolyte is polyoxyethylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate or Kynoar in the step 5.Other step and parameter are identical with one of embodiment 14 to 37.
Type of polymer is different in the present embodiment, and it is also different to make that then polymer is in liquid required temperature, and the temperature of therefore controlling in the container can be decided according to the kind of the polymer of concrete employing.
Embodiment 39: what this execution mode was different with one of embodiment 14 to 38 is in the step 6 porous ceramic matrices suitable after step 5 is handled to be solidified 12 ~ 18min at ambient temperature.Other step and parameter are identical with one of embodiment 14 to 38.
Embodiment 40: what this execution mode was different with one of embodiment 14 to 38 is in the step 6 porous ceramic matrices suitable after step 5 is handled to be solidified 15min at ambient temperature.Other step and parameter are identical with one of embodiment 14 to 38.
Embodiment 41: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 80% solid polymer electrolyte and 20% aluminium oxide; The aluminium oxide that aluminium oxide continuous directional profile mutually wherein, solid polymer electrolyte evenly are filled in directional profile mutually in; Contain mass percent in the said solid polymer electrolyte and be 8% LiClO
4
Polymer in this execution mode in the solid polymer electrolyte is a polyoxyethylene.
This execution mode adopts the means of testing of three-point bending and monolateral otch method that pottery/solid polymer electrolyte composite material is carried out Mechanics Performance Testing; Adopt the means of testing of alternating current bridge method that pottery/solid polymer electrolyte composite material is carried out the conductivity test; Test result is: three-point bending strength reaches 110MPa, and fracture toughness reaches 2.3MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 3.15 * 10
-5S/cm.
Embodiment 42: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 90% solid polymer electrolyte and 10% aluminium oxide; The aluminium oxide that aluminium oxide continuous directional profile mutually wherein, solid polymer electrolyte evenly are filled in directional profile mutually in; Contain mass percent in the said solid polymer electrolyte and be 5% LiBF
4
Polymer in this execution mode in the solid polymer electrolyte is a polyacrylonitrile.
The means of testing that this execution mode adopts embodiment No. 41 Institute to state carries out the test of mechanical property and conductivity to pottery/solid polymer electrolyte composite material, and test result is: three-point bending strength reaches 102MPa, and fracture toughness reaches 2.1MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 1.05 * 10
-5S/cm.
Embodiment 43: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 90% solid polymer electrolyte and 10% zirconia; The zirconia that zirconia continuous directional profile mutually wherein, solid polymer electrolyte evenly are filled in directional profile mutually in; Contain mass percent in the said solid polymer electrolyte and be 4% LiClO
4
Polymer in this execution mode in the solid polymer electrolyte is a polymethyl methacrylate.
The means of testing that this execution mode adopts embodiment No. 41 Institute to state carries out the test of mechanical property and conductivity to pottery/solid polymer electrolyte composite material, and test result is: three-point bending strength reaches 109MPa, and fracture toughness reaches 2.2MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 2.09 * 10
-6S/cm S/cm.
Embodiment 44: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 60% solid polymer electrolyte and 40% zirconia; The zirconia that zirconia continuous directional profile mutually wherein, solid polymer electrolyte evenly are filled in directional profile mutually in; Contain mass percent in the said solid polymer electrolyte and be 5% LiPF
6
Polymer in this execution mode in the solid polymer electrolyte is a Kynoar.
The means of testing that this execution mode adopts embodiment No. 41 Institute to state carries out the test of mechanical property and conductivity to pottery/solid polymer electrolyte composite material, and test result is: three-point bending strength reaches 121MPa, and fracture toughness reaches 2.9MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 4.51 * 10
-6S/cm.
Embodiment 45: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 90% solid polymer electrolyte and 10% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain the LiAsF that mass percent is 6 % in the said solid polymer electrolyte
6Said solid phase is made up of beta-silicon nitride powder and sintering aid, and wherein the sintering aid quality accounts for 6% of solid phase gross mass, and sintering aid is Y
2O
3-MgO.
Polymer in this execution mode in the solid polymer electrolyte is a polyoxyethylene.Y in the sintering aid
2O
3Mix with any mass ratio with MgO.
The means of testing that this execution mode adopts embodiment No. 41 Institute to state carries out the test of mechanical property and conductivity to pottery/solid polymer electrolyte composite material, and test result is: three-point bending strength reaches 101MPa, and fracture toughness reaches 2.0MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 8.41 * 10
-6S/cm.
Embodiment 46: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 60% solid polymer electrolyte and 40% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain the LiClO that mass percent is 9 % in the said solid polymer electrolyte
4Said solid phase is made up of silicon carbide powder and sintering aid, and wherein the sintering aid quality accounts for 6% of solid phase gross mass, and sintering aid is BaO-Al
2O
3-SiO
2
Polymer in this execution mode in the solid polymer electrolyte is a polyvinyl chloride.BaO, Al in the sintering aid
2O
3And SiO
2Mix with any mass ratio.
The sem photograph in the vertical section of pottery/solid polymer electrolyte composite material that the wild phase continuously-directional of this execution mode distributes is as shown in Figure 3, and black part is divided into solid phase among the figure, and grey color part is a solid polymer electrolyte; Visible by Fig. 3, the solid phase continuously-directional distributes in pottery/solid polymer electrolyte composite material, and solid polymer electrolyte evenly is filled in the solid phase of directional profile.The cross section sem photograph of pottery/solid polymer electrolyte composite material is as shown in Figure 4, and black part is divided into solid phase among the figure, and grey color part is a solid polymer electrolyte.
The means of testing that this execution mode adopts embodiment No. 41 Institute to state carries out the test of mechanical property and conductivity to pottery/solid polymer electrolyte composite material, and test result is: three-point bending strength reaches 146MPa, and fracture toughness reaches 3.8MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 6.16 * 10
-5S/cm.
Embodiment 47: pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes by volume percentage is made up of 70% solid polymer electrolyte and 30% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain the LiClO that mass percent is 4 % in the said solid polymer electrolyte
4Said solid phase is made up of beta-silicon nitride powder and sintering aid, and wherein the sintering aid quality accounts for 6% of solid phase gross mass, and sintering aid is Y
2O
3-MgO-CaO.
Polymer in this execution mode in the solid polymer electrolyte is polyoxyethylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate or Kynoar.Y in the sintering aid
2O
3, MgO and CaO mix with any mass ratio.
The means of testing that this execution mode adopts embodiment No. 41 Institute to state carries out the test of mechanical property and conductivity to pottery/solid polymer electrolyte composite material, and test result is: three-point bending strength reaches 136MPa, and fracture toughness reaches 3.1MPam
1/2The continuous mutually directional profile of aluminium oxide makes the conductivity of pottery/solid polymer electrolyte composite material improve, and room-temperature conductivity has reached 1.31 * 10
-6S/cm.
Embodiment 48: the preparation method of pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes; Realize through following steps: one, alumina powder jointed, dispersant polyacrylic acid and deionized water are mixed; Ball milling 24h then obtains solid volume content and is 20% slurry, wherein; Solid phase is alumina powder jointed, and the polyacrylic quality of dispersant is 0.06% of an alumina powder jointed quality; Two, the slurry that step 1 is obtained injects mould; After leaving standstill 20min; Condition bottom knockout at-5 ℃ obtains the solid-state ceramic matrix, and wherein the base material of mould is a brass, and the brass of mould bottom is immersed in-70 ℃ ~-60 ℃ the mixed liquor coolant of ethylene glycol and liquid nitrogen; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 48h, and then under 80 ℃ condition dry 2h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-30 ℃; Four, with the porous ceramic matrices suitable base substrate at 1600 ℃ of sintering 3h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; Then with seal of vessel; Again container is evacuated to 0.1Pa, under the pressure of 0.1Pa, keeps 8min then, wherein contain the LiClO that mass percent is 8 % in the liquid polymer electrolyte
4, keeping the interior temperature of container is 70 ~ 80 ℃; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 10 ~ 20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
In this execution mode step 2 in the coolant ethylene glycol and liquid nitrogen be the mixed of 5:1 with the volume ratio.Polymer is a polyoxyethylene in the step 5, under 70 ℃, can remain liquid state.The mould structure that uses in this execution mode step 2 is as shown in Figure 1; Vacuum hotpressing power infiltrate journey is accomplished in equipment as shown in Figure 2 in the step 5.
Pottery/solid polymer electrolyte composite material that this execution mode prepares is consistent with the composite material of embodiment 41.
Embodiment 49: the preparation method of pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes; Realize through following steps: one, Zirconium powder, dispersant polyacrylic acid and deionized water are mixed; Ball milling 24h then obtains solid volume content and is 40% slurry, wherein; Solid phase is a Zirconium powder, and the polyacrylic quality of dispersant is 0.04% of a Zirconium powder quality; Two, the slurry that step 1 is obtained injects mould; After leaving standstill 20min; Condition bottom knockout at-5 ℃ obtains the solid-state ceramic matrix, and wherein the base material of mould is a brass, and the brass of mould bottom is immersed in-50 ℃ ~-40 ℃ the mixed liquor coolant of glycerine and liquid nitrogen; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 48h, and then under 80 ℃ condition dry 2h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-30 ℃; Four, with the porous ceramic matrices suitable base substrate at 1500 ℃ of sintering 3h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; Then with seal of vessel; Again container is evacuated to 0.1Pa, under the pressure of 0.1Pa, keeps 8min then, wherein contain the LiPF that mass percent is 5 % in the liquid polymer electrolyte
6, keeping the interior temperature of container is 170 ~ 180 ℃; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
In this execution mode step 2 in the coolant ethylene glycol and liquid nitrogen be the mixed of 8:1 with the volume ratio.Polymer is a Kynoar in the step 5, under 170 ℃, can remain liquid state.The mould structure that uses in this execution mode step 2 is as shown in Figure 1; Vacuum hotpressing power infiltrate journey is accomplished in equipment as shown in Figure 2 in the step 5.
Pottery/solid polymer electrolyte composite material that this execution mode prepares is consistent with the composite material of embodiment 44.
Embodiment 50: the preparation method of pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes, realize through following steps: one, with beta-silicon nitride powder, sintering aid Y
2O
3-MgO, dispersant polyacrylic acid and deionized water mix; Ball milling 24h then; Obtain solid volume content and be 10% slurry, wherein, solid phase is beta-silicon nitride powder and sintering aid; The quality of sintering aid accounts for 6% of solid phase gross mass, and the polyacrylic quality of dispersant is 0.05% of a ceramic powder quality; Two, the slurry that step 1 is obtained injects mould, leave standstill 30min after, obtain the solid-state ceramic matrix-10 ℃ condition bottom knockouts, wherein the base material of mould is a heat-conducting metal brass, the brass bottom of mould is immersed in-196 ℃ the liquid nitrogen frozen medium; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 60h, and then under 80 ℃ condition dry 1.5h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-25 ℃; Four, with the porous ceramic matrices suitable base substrate at 1800 ℃ of sintering 1h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; Then with seal of vessel; Again container is evacuated to 0.6Pa, under the pressure of 0.6Pa, keeps 12min then, wherein contain mass percent in the liquid polymer electrolyte and be 6% LiAsF
6, keeping the interior temperature of container is 70 ~ 80 ℃; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
Y in the sintering aid in this execution mode step 1
2O
3Mix with any mass ratio with MgO.Polymer is a polyoxyethylene in the step 5, under 70 ℃, can remain liquid state.The mould structure that uses in this execution mode step 2 is as shown in Figure 1; Vacuum hotpressing power infiltrate journey is accomplished in equipment as shown in Figure 2 in the step 5.
Pottery/solid polymer electrolyte composite material that this execution mode prepares is consistent with the composite material of embodiment 45.
Embodiment 51: the preparation method of pottery/solid polymer electrolyte composite material that this execution mode wild phase continuously-directional distributes, realize through following steps: one, with silicon carbide powder, sintering aid BaO-Al
2O
3-SiO
2, dispersant polyacrylic acid and deionized water mix, ball milling 24h then obtains solid volume content and is 40% slurry; Wherein, Solid phase is silicon carbide powder and sintering aid, and the quality of sintering aid accounts for 6% of solid phase gross mass, and the polyacrylic quality of dispersant is 0.06% of a ceramic powder quality; Two, the slurry that step 1 is obtained injects mould; After leaving standstill 30min; Condition bottom knockout at-10 ℃ obtains the solid-state ceramic matrix, and wherein the base material of mould is a heat-conducting metal brass, and the brass of mould bottom is immersed in-120 ℃ ~-100 ℃ the mixed liquor refrigerant of alcohol and liquid nitrogen; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 60h, and then under 80 ℃ condition dry 2h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-25 ℃; Four, with the porous ceramic matrices suitable base substrate at 1700 ℃ of sintering 2h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; Then with seal of vessel; Again container is evacuated to 0.6Pa, under the pressure of 0.6Pa, keeps 12min then, wherein contain mass percent in the liquid polymer electrolyte and be 9% LiClO
4, keeping the interior temperature of container is 170 ~ 180 ℃; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
Y in the sintering aid in this execution mode step 1
2O
3Mix with any mass ratio with MgO.In the step 2 in the coolant alcohol and liquid nitrogen be the mixed of 3:1 with the volume ratio.Polymer is a polyvinyl chloride in the step 5, under 170 ℃, can remain liquid state.The mould structure that uses in this execution mode step 2 is as shown in Figure 1; Vacuum hotpressing power infiltrate journey is accomplished in equipment as shown in Figure 2 in the step 5.
Pottery/solid polymer electrolyte composite material that this execution mode prepares is consistent with the composite material of embodiment 46.The sem photograph in the vertical section of pottery/solid polymer electrolyte composite material that this execution mode prepares (promptly prolong the temperature gradient direction, also promptly be parallel to the ice-crystal growth method) is consistent with Fig. 3; The sem photograph in the cross section of composite material (promptly perpendicular to temperature gradient method, also promptly perpendicular to the ice-crystal growth method) is consistent with Fig. 4.
Claims (8)
1. pottery/solid polymer electrolyte composite material of distributing of a wild phase continuously-directional; It is characterized in that pottery/solid polymer electrolyte composite material that the wild phase continuously-directional distributes by volume percentage form by 60%～90% solid polymer electrolyte and 10%～40% solid phase; Wherein the solid phase continuously-directional distributes, and solid polymer electrolyte evenly is filled in the solid phase of directional profile; Contain mass percent in the said solid polymer electrolyte and be 4%～9% lithium salts; Said solid phase is made up of ceramic powder and sintering aid, and wherein the sintering aid quality accounts for 1%～10% of solid phase gross mass, and sintering aid is MgO, CaO, BaO, Li
2O, TiO
2, AlN, Y
2O
3, Al
2O
3, La
2O
3, Yb
2O
3, Ce
2O
3, Nd
2O
3And SiO
2In a kind of or several kinds composition wherein; Ceramic powder is carborundum or silicon nitride.
2. pottery/solid polymer electrolyte composite material that a kind of wild phase continuously-directional according to claim 1 distributes is characterized in that the lithium salts in the solid polymer electrolyte is LiClO
4, LiBF
4, LiAsF
6, LiPF
6, LiCF
3SO
3, Li (CF
3SO
2)
2Perhaps LiN (CF
3SO
2)
2
3. pottery/solid polymer electrolyte composite material that a kind of wild phase continuously-directional according to claim 1 and 2 distributes is characterized in that the polymer in the solid polymer electrolyte is polyoxyethylene, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate or Kynoar.
4. pottery/solid polymer electrolyte composite material that a kind of wild phase continuously-directional according to claim 1 and 2 distributes; It is characterized in that said solid phase only is made up of ceramic powder, said ceramic powder is aluminium oxide, zirconia, hydroxyapatite or mullite.
5. the preparation method of pottery/solid polymer electrolyte composite material that a kind of wild phase continuously-directional as claimed in claim 1 distributes; The preparation method who it is characterized in that pottery/solid polymer electrolyte composite material that the wild phase continuously-directional distributes realizes through following steps: one, ceramic powder, sintering aid, dispersant polyacrylic acid and deionized water are mixed; Ball milling 20～30h then; Obtain solid volume content and be 10%～40% slurry; Wherein, solid phase is ceramic powder and sintering aid, and the quality of sintering aid accounts for 1%～10% of solid phase gross mass; The polyacrylic quality of dispersant is 0.04%～0.06% of a ceramic powder quality, and said sintering aid is MgO, CaO, BaO, Li
2O, TiO
2, AlN, Y
2O
3, Al
2O
3, La
2O
3, Yb
2O
3, Ce
2O
3, Nd
2O
3And SiO
2In a kind of or several kinds composition wherein; Ceramic powder is carborundum or silicon nitride; Two, the slurry that step 1 is obtained injects mould; After leaving standstill 10～30min; Condition bottom knockout being lower than 0 ℃ obtains the solid-state ceramic matrix, and wherein the base material of mould is a heat-conducting metal, and the heat-conducting metal of mould bottom is immersed in-200 ℃～-60 ℃ the refrigerant; Three, the solid-state ceramic matrix that step 2 is obtained is put into freeze dryer freeze drying 24～72h, and then under 60～80 ℃ condition dry 1～2h, obtain the porous ceramic matrices suitable base substrate, wherein freeze drying temperature is-20 ℃～-30 ℃; Four, with the porous ceramic matrices suitable base substrate at 1500～1800 ℃ of sintering 1～3h, obtain continuously-directional distributed porous ceramic matrix; Five, the porous ceramic matrices suitable that step 4 is obtained is put into the electrolytical container of liquid polymer is housed; And be immersed in the liquid polymer electrolyte; With seal of vessel, again container is evacuated to 0.1～1Pa then, under the pressure of 0.1～1Pa, keeps 8～15min then; Wherein contain mass percent in the liquid polymer electrolyte and be 4%～9% lithium salts, keep that temperature is 70～180 ℃ in the container; Six, the porous ceramic matrices suitable after step 5 is handled is solidified 10～20min at ambient temperature, promptly get ceramic/solid polymer electrolyte composite material.
6. the preparation method of pottery/solid polymer electrolyte composite material that a kind of wild phase continuously-directional according to claim 5 distributes; It is characterized in that solid phase only is made up of ceramic powder in the step 1, said ceramic powder is aluminium oxide, zirconia, hydroxyapatite or mullite.
7. the preparation method of the pottery/solid polymer electrolyte composite material that distributes according to claim 5 or 6 described a kind of wild phase continuously-directionals is characterized in that refrigerant in the step 2 is a kind of in liquid nitrogen, liquid helium, alcohol, glycerine solvent or the ethylene glycol solvent or several kinds mixture wherein.
8. the preparation method of pottery/solid polymer electrolyte composite material that a kind of wild phase continuously-directional according to claim 7 distributes is characterized in that the lithium salts in the liquid polymer electrolyte is LiClO in the step 5
4, LiBF
4, LiAsF
6, LiPF
6, LiCF
3SO
3, Li (CF
3SO
2)
2Perhaps LiN (CF
3SO
2)
2
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| CN104235237B (en) * | 2014-05-09 | 2017-05-10 | 石家庄东大汇通新材料有限公司 | Brake disc made of carborundum foamed ceramics/aluminum alloy composite materials and production method of road vehicle brake disc |
| CN107261866A (en) * | 2017-08-10 | 2017-10-20 | 武汉纺织大学 | A kind of preparation method of through hole membrane for water treatment |
| CN108994300B (en) * | 2018-07-03 | 2021-03-26 | 中国科学院金属研究所 | Carbon/metal composite material with micro-oriented structure for electric contact and preparation method thereof |
| CN108994301B (en) * | 2018-07-03 | 2021-03-26 | 中国科学院金属研究所 | Metal-based bionic composite material reinforced by nano carbon material and preparation method thereof |
| CN110336073A (en) * | 2019-07-04 | 2019-10-15 | 北京协同创新研究院 | A kind of solid electrolyte and preparation method thereof, solid state battery and electronic equipment |
| TWI719683B (en) * | 2019-10-22 | 2021-02-21 | 輝能科技股份有限公司 | Ceramic separator |
| CN113270634A (en) * | 2021-04-14 | 2021-08-17 | 华南师范大学 | Composite solid electrolyte based on inorganic ceramic three-dimensional aerogel framework support and preparation method thereof |
| CN113300058B (en) * | 2021-04-28 | 2022-11-04 | 湖南立方新能源科技有限责任公司 | Liquid injection method of lithium battery, manufacturing method of lithium battery and lithium battery |
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