CN108609659A - A kind of semiconductive composite material and preparation method of modification - Google Patents
A kind of semiconductive composite material and preparation method of modification Download PDFInfo
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- CN108609659A CN108609659A CN201810547838.0A CN201810547838A CN108609659A CN 108609659 A CN108609659 A CN 108609659A CN 201810547838 A CN201810547838 A CN 201810547838A CN 108609659 A CN108609659 A CN 108609659A
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 230000004048 modification Effects 0.000 title claims abstract description 70
- 238000012986 modification Methods 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010416 ion conductor Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 15
- -1 rare earth manganese oxide Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 150000001768 cations Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000007500 overflow downdraw method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910002254 LaCoO3 Inorganic materials 0.000 description 3
- 229910002328 LaMnO3 Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910002331 LaGaO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019336 PrMnO3 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910010389 TiMn Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002226 superionic conductor Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/70—Cobaltates containing rare earth, e.g. LaCoO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Conductive Materials (AREA)
- Inert Electrodes (AREA)
Abstract
This application involves a kind of semiconductive composite material and preparation methods of modification, belong to electrical material field.The semiconductive composite material of the modification of the application, wherein the fast-ionic conductor containing the modification with cationic hole.The preparation method of the semiconductive composite material of the modification of the application comprising, the fast-ionic conductor of the modification with cationic hole is added in semiconductive composite material, modified semiconductive composite material is prepared；It is mainly used for high-tension cable, realizes the effect for reducing charge emission in semiconductive composite material.
Description
Technical field
This application involves a kind of semiconductive composite material and preparation methods of modification, belong to electrical material field.
Background technology
Semiconductive composite material is widely used in high-tension cable, such as uniform electric field is played between conductor and insulating layer
Effect.Especially in high voltage direct current cable, due to accumulation space charge in insulating layer, electric field distortion is easily caused, aging is caused
Accelerate even to puncture.Numerous studies show that charge is from not only metal core in cable insulation, with semiconductive composite material
Charge emission is also closely related.Therefore, the modification for studying semiconductive composite material, to reducing its charge emission and PTC
Charge buildup is of great significance in (Positive Temperature Coefficient) effect, reduction insulating layer.
Conventional use of semiconductive composite material has but is not limited to, such as mainly by ethylene-vinyl acetate copolymer
(EVA), semiconductive composite material made from carbon black and polyethylene (especially low density polyethylene).Currently, research is partly led
Composite be modified mainly with change the modified material based on carbon black doping ratio, obtained in this way its reduce charge emission,
It is not particularly evident to reduce PTC effects, reduce the effect of charge buildup in insulating layer.
Invention content
The application's is designed to provide a kind of semiconductive composite material and preparation method of modification, is mainly used for high pressure
Cable realizes the effect for reducing charge emission in semiconductive composite material.
A kind of embodiment of the application provides a kind of semiconductive composite material of modification, wherein containing having cation
The fast-ionic conductor of the modification in hole.
As a preferred embodiment, being ABX by using chemical formula3Perovskite structure, by the A in its structure
Bit element is replaced using the metallic element C of more low price, and/or, by the B bit elements in its structure using the metal of more low price
Element D is replaced, to obtain the fast-ionic conductor of the modification.
The replacement can be part be replaced can also be all be replaced, be preferably partly replaced.
Second of embodiment of the application provides a kind of preparation method of the semiconductive composite material of modification, packet
It includes, the fast-ionic conductor of the modification with cationic hole is added in semiconductive composite material to be prepared and modified is partly led
Composite.
As a preferred embodiment, specifically, the preparation method includes：
By perovskite structure ABX3In A bit elements replaced using the metallic element C of more low price, and/or, will be in structure
B bit elements replaced using the metallic element D of more low price, modified fast-ionic conductor is prepared；
The fast-ionic conductor for the modification being prepared is added in semiconductive composite material, it is multiple to obtain modified semiconductive
Condensation material.
Compared with prior art, the application has the beneficial effect that：
It is added in semiconductive composite material using modified fast-ionic conductor as additive, obtained composite material is not
Only inhibit the charge injection can to inhibit the PTC effects of composite material due also to ionic conductivity increases, therefore this method carries
The further investigation and production domesticization for going out double conducing composite material are of great significance.
Description of the drawings
Fig. 1 is the schematic diagram of the perovskite structure of the prior art；
Fig. 2 is the schematic diagram of the perovskite structure of embodiment 1；
Fig. 3 is the schematic diagram of the fast-ionic conductor of the modification of embodiment 1.
Specific implementation mode
Full and accurate elaboration is carried out to the technical solution of the application below in conjunction with specific implementation mode, it being understood, however, that
In the case of not being further discussed below, structure or feature in an embodiment can also be advantageously incorporated into other embodiment party
In formula.
In the description of the present application, it should be noted that term " first ", " second " etc. are used for description purposes only, without
It can be interpreted as indicating or implying relative importance.The embodiment is only to be retouched to the preferred embodiment of the application
It states, not scope of the present application is defined, under the premise of not departing from the application design spirit, ordinary skill people
The various modifications and improvement that member makes the technical solution of the application, should all fall into the protection model of the application claims determination
In enclosing.
Term use herein, is defined as follows in the prior art：
(1) fast-ionic conductor (fast ionic conductor) is also referred to as superionic conductors, is called sometimes and does solid electrolytic
Matter, the most basic feature that it is different from general ion conductor be within the scope of certain temperature have can be compared with liquid electrolyte
Quasi- ionic conductivity (1*10-6S·cm-1) and low ionic conductance activation energy (≤0.40eV).
(2) perovskite composite oxide (referred to as perovskite structure) is structure and perovskite CaTiO3Identical one is big
Class compound, perovskite structure can use ABX3Indicate, wherein A be alkaline earth element, cation be in 12 coordination structures, positioned at by
In the hole that octahedron is constituted；B are transition metal element, and cation forms octahedral coordination with six oxonium ions, and X are oxygen
Element, structure are as shown in Figure 1.
It is worth noting that：The application is using perovskite structure ABX3When this concept, the main knot using similar Fig. 1
Structure, but alkaline earth element is not limited to for A bit elements, B bit elements are not limited to transition metal element, and X bits element is not
It is confined to as oxygen element.
A kind of embodiment of the application provides a kind of semiconductive composite material of modification, wherein containing having cation
The fast-ionic conductor of the modification in hole.
As a preferred embodiment, by using perovskite structure, chemical formula ABX3, by the A in its structure
Bit element is replaced using the metallic element C of more low price, and/or, by the B bit elements in its structure using the metal of more low price
Element D is replaced, to obtain modified fast-ionic conductor.
The replacement can be part be replaced can also be all be replaced, be preferably partly replaced.It is described
ABX3A bits element and/or B bits element the stability of holding structure is remained to after all or part of replaced.
As a preferred embodiment, the metallic element C can be alkaline-earth metal or transition metal, the metal
Element D can be alkaline-earth metal or transition metal.The application is mainly to substitute high price A bits using the metallic element of low price
Element and/or B bits element such as can be used divalent Sr (C) and substitute trivalent La (A), after replacement, since the presence of price difference to be modified
Fast-ionic conductor in form cation vacancy, so as to inhibit the injection of negative electrical charge.
As a preferred embodiment, the X bits element in the perovskite structure can be oxygen element (O), fluorine member
Plain (F) or chlorine element (Cl), i.e. perovskite structure can be ABO3、ABF3Or ABCl3。
As a preferred embodiment, the perovskite structure is perovskite rare earth manganese oxide, expression formula
For RMnO3, wherein R is trivalent rare earth element, is perovskite structure ABX3In A bits element, Mn is B bit elements, and O is X bits
Element.
The R is preferably the trivalent rare earth elements such as La, Nd, Pr, Tb, i.e., perovskite structure can be LaMnO3、NdMnO3、
PrMnO3Or TbMnO3。
At this point, since R is trivalent rare earth element, the metallic element C for being accordingly used in substituting is preferably divalent metal element, such as
The divalent metals such as Ca, Sr, Ba.
As a preferred embodiment, the fast-ionic conductor of the modification is using sol-gal process, solid fusion method
The methods of be made, that is, use sol-gal process or solid fusion method by the A bit elements in perovskite structure using more low price
Metallic element C is replaced, and/or, the B bit elements in structure are replaced using the metallic element D of more low price, are prepared modified
Fast-ionic conductor.
As a preferred embodiment, the fast-ionic conductor of the modification is in modified semiconductive composite material
Mass percent is 0.1%-20%；For example, can be 0.5%, 1%, 2%, 5%, 6%, 8%, 10%, 12%, 14%,
15%, 18%, 20% etc.；Particularly preferred mass percent is 3%-15%, and particularly preferred mass percent is 10% or so.
As a preferred embodiment, the fast-ionic conductor of the modification is ultra-fine fast-ionic conductor, described is super
The diameter for the fast-ionic conductor that microdactylia is modified is usually more than 1 μm, generally hundreds of nanometers.
Second of embodiment of the application provides a kind of preparation method of the semiconductive composite material of modification and (below may be used
Referred to as preparation method), step includes that it is compound that the fast-ionic conductor of the modification with cationic hole is added to semiconductive
Modified semiconductive composite material is prepared in material.
As a preferred embodiment, specifically, the preparation method includes：
By perovskite structure ABX3In A bit elements replaced using the metallic element C of more low price, and/or, will be in structure
B bit elements replaced using the metallic element D of more low price, modified fast-ionic conductor is prepared；
The fast-ionic conductor for the modification being prepared is added in semiconductive composite material, it is multiple to obtain modified semiconductive
Condensation material.
As a preferred embodiment, the ABX3In A bits element and/or B bit elements replaced by metallic element
When, it is realized using sol-gal process or solid fusion method.
As a preferred embodiment, surface modification is carried out to the fast-ionic conductor for the modification being prepared, it is described
Surface is modified to refer to adds surface dispersant in modified fast-ionic conductor, to reach best dispersion effect.
The surface dispersant can select cetyl trimethylammonium bromide, polymethylacrylic acid, polyethyleneimine or
Isopropyl triisostearoyltitanate.It is preferred that quality accounting of the surface dispersant in modified semiconductive composite material is not
More than 1%；May be, for example, 1%, 0.9%, 0.85%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%,
0.1% etc..
The application is explained in detail with reference to embodiments, it is to be understood that due to can be used for the A of the application
Bit element, B bit elements, and it is substituted for the specific element that the metallic element C and metallic element D of effect can be selected
Too many, the application is at all impossible to exhaust, therefore only several in selection example, for illustratively showing the application, institute
These elements of selection can not be interpreted as the limitation to the protection domain of the application.
Embodiment 1
S1：Choose perovskite structure LaMnO3, as shown in Fig. 2, realizing LaMnO using sol-gal process or solid fusion method3
Middle part La3+By Sr2+Substitution, to form cation vacancy；The fast-ionic conductor of modification as shown in Figure 3 is prepared
La1-xSrxMnO3-z, wherein x and z are that chemical bond matches potential coefficient；
For the situation in Fig. 3, since 2 La are replaced by Sr, x=2/8=0.25,1-x=0.75, and due to La
For+trivalent, Sr is+divalent, and Mn is+trivalent, and O is-divalent, therefore by 0.75*3+0.25*2+1*3- (3-z) * 2=0, obtains z=
0.125, the structural formula to obtain modified fast-ionic conductor is La0.75Sr0.25MnO2.875。
S2：The fast-ionic conductor for the modification being prepared is added in semiconductive composite material, to obtain modification
Semiconductive composite material；Wherein, quality accounting of the fast-ionic conductor of the modification in modified semiconductive composite material is
12%.
Embodiment 2
S1：Choose perovskite structure LaMnO3, LaMnO is realized using sol-gal process or solid fusion method3Middle La3+All
By Sr2+Substitution, to form cation vacancy；Modified fast-ionic conductor SrMnO is prepared3-z, wherein z=0.5；
S2：The fast-ionic conductor for the modification being prepared is added in semiconductive composite material, to obtain modification
Semiconductive composite material；Wherein, quality accounting of the fast-ionic conductor of the modification in modified semiconductive composite material is
10%.
Embodiment 3
On the basis of embodiment 1, surface dispersant is added in the fast-ionic conductor for the modification being prepared in S1 steps
Cetyl trimethylammonium bromide, to carry out surface modification to modified fast-ionic conductor；And by the modified modification in surface
Fast-ionic conductor be added in semiconductive composite material, the semiconductive composite material being modified accordingly；Wherein, surface point
Quality accounting of the powder in modified semiconductive composite material is 1%.
In the present embodiment, surface dispersant can make the dispersion effect of modified fast-ionic conductor more preferably, so that
The semiconductive composite material of obtained modification is more uniform.
Embodiment 4
S1：Choose perovskite structure LaCoO3, LaCoO is realized using sol-gal process or solid fusion method3Middle part La quilts
Sr replaces, to form cation vacancy；Modified fast-ionic conductor La is prepared1-xSrxCoO3-z；
S2：Surface dispersant polymethylacrylic acid is added into the fast-ionic conductor for the modification being prepared, to changing
Property fast-ionic conductor carry out surface modification；
S3：The fast-ionic conductor of the modified modification in surface is added in semiconductive composite material, to be modified
Semiconductive composite material.
Wherein, modified fast-ionic conductor quality accounting in modified semiconductive composite material is 10%, Dispersion on surface
Agent quality accounting in modified semiconductive composite material is 0.8%.
Embodiment 5
S1：Choose perovskite structure LaCoO3, LaCoO is realized using sol-gal process or solid fusion method3Middle part Co quilts
Fe replaces, to form cation vacancy；Modified fast-ionic conductor LaCo is prepared1-yFeyO3-z；
S2：Surface dispersant polyethyleneimine is added into the fast-ionic conductor for the modification being prepared, to modification
Fast-ionic conductor carry out surface modification；
S3：The fast-ionic conductor of the modified modification in surface is added in semiconductive composite material, to be modified
Semiconductive composite material.
Wherein, modified fast-ionic conductor quality accounting in modified semiconductive composite material is 15%, Dispersion on surface
Agent quality accounting in modified semiconductive composite material is 0.9%.
Embodiment 6
S1：Choose perovskite structure KMnF3, KMnF is realized using sol-gal process or solid fusion method3In part Mn quilts
Fe replaces, and to form cation vacancy, modified fast-ionic conductor KMn is prepared1-yFeyF3-z；
S2：Three isostearoyl base metatitanic acid isopropyl of surface dispersant is added into the fast-ionic conductor for the modification being prepared
Ester, to carry out surface modification to modified fast-ionic conductor；
S3：The fast-ionic conductor of the modified modification in surface is added in semiconductive composite material, to be modified
Semiconductive composite material.
Wherein, modified fast-ionic conductor quality accounting in modified semiconductive composite material is 3%, surface dispersant
Quality accounting is 1% in modified semiconductive composite material.
Embodiment 7
S1：Choose perovskite structure TiMnCl3, TiMnCl is realized using sol-gal process or solid fusion method3In part
Mn is replaced by Fe, and to form cation vacancy, modified fast-ionic conductor TiMn is prepared1-yFeyCl3-z；
S2：Three isostearoyl base metatitanic acid isopropyl of surface dispersant is added into the fast-ionic conductor for the modification being prepared
Ester, to carry out surface modification to modified fast-ionic conductor；
S3：The fast-ionic conductor of the modified modification in surface is added in semiconductive composite material, to be modified
Semiconductive composite material.
Wherein, modified fast-ionic conductor quality accounting in modified semiconductive composite material is 10%, Dispersion on surface
Agent quality accounting in modified semiconductive composite material is 1%.
Embodiment 8
S1：Choose perovskite structure LaCoO3, LaCoO is realized using sol-gal process or solid fusion method3Middle part La quilts
Sr replaces, and part Co is replaced by Fe, and to form cation vacancy, modified fast-ionic conductor La is prepared1-xSrxCo1- yFeyO3-z；
S2：Three isostearoyl base metatitanic acid isopropyl of surface dispersant is added into the fast-ionic conductor for the modification being prepared
Ester, to carry out surface modification to modified fast-ionic conductor；
S3：The fast-ionic conductor of the modified modification in surface is added in semiconductive composite material, to be modified
Semiconductive composite material.
Wherein, modified fast-ionic conductor quality accounting in modified semiconductive composite material is 10%, Dispersion on surface
Agent quality accounting in modified semiconductive composite material is 1%.
Embodiment 9
S1：Choose perovskite structure LaGaO3, LaGaO is realized using sol-gal process or solid fusion method3In part La
Replaced by Sr, the parts Ga are replaced by Mg, and to form cation vacancy, modified fast-ionic conductor La is prepared1- xSrxGa1-yMgyO3-z；
S2：Three isostearoyl base metatitanic acid isopropyl of surface dispersant is added into the fast-ionic conductor for the modification being prepared
Ester, to carry out surface modification to modified fast-ionic conductor；
S3：The fast-ionic conductor of the modified modification in surface is added in semiconductive composite material, to be modified
Semiconductive composite material.
Wherein, modified fast-ionic conductor quality accounting in modified semiconductive composite material is 10%, Dispersion on surface
Agent quality accounting in modified semiconductive composite material is 1%.
Contrast and experiment：
Below by way of to ethylene-vinyl acetate copolymer (EVA), carbon black and polyethylene (referred to as EVA/LDPE/CB)
Semiconductive composite material obtained is modified, to illustrate the superiority of the application.
For semiconductive composite material in the prior art, when carbon black (CB) is 25%, the inhibition charge that can be reached injects
Effect and PTC effect inhibitions are best.The application by A, B, C, D gear come evaluate inhibit charge inject effect and
PTC effect inhibitions, wherein A+ are best, and D- is worst.
Table 1：Experimental result contrast table
Claims (10)
1. a kind of semiconductive composite material of modification, which is characterized in that wherein contain the modification with cationic hole it is fast from
Sub- conductor.
2. the semiconductive composite material of modification according to claim 1, which is characterized in that by using chemical formula be ABX3
Perovskite structure, the A bit elements in its structure are replaced using the metallic element C of more low price, and/or, will be in its structure
B bit elements replaced using the metallic element D of more low price, to obtain the fast-ionic conductor of the modification.
3. the semiconductive composite material of modification according to claim 2, which is characterized in that replace the part that replaces with
It changes；The metallic element C is alkaline-earth metal or transition metal, and the metallic element D is alkaline-earth metal or transition metal.
4. the semiconductive composite material of modification according to claim 2, which is characterized in that the X in the perovskite structure
Bit element is oxygen element (O), fluorine element (F) or chlorine element (Cl).
5. the semiconductive composite material of modification according to claim 2 or 3, which is characterized in that the perovskite structure is
Perovskite rare earth manganese oxide, expression formula RMnO3, wherein R is trivalent rare earth element.
6. according to claim 1-4 any one of them be modified semiconductive composite material, which is characterized in that the modification it is fast
Mass percent of the ion conductor in modified semiconductive composite material is 0.1%-20%.
7. according to claim 1-4 any one of them be modified semiconductive composite material, which is characterized in that the modification it is fast
Ion conductor is ultra-fine fast-ionic conductor, and the diameter for the fast-ionic conductor that the ultra-fine finger is modified is not more than 1 μm.
8. a kind of preparation method of the semiconductive composite material of modification, step include, by the modification with cationic hole
Fast-ionic conductor, which is added in semiconductive composite material, is prepared modified semiconductive composite material.
9. preparation method according to claim 8, which is characterized in that specifically, the preparation method includes：
By perovskite structure ABX3In A bit elements replaced using the metallic element C of more low price, and/or, by the positions B in structure
Element is replaced using the metallic element D of more low price, and modified fast-ionic conductor is prepared；
The fast-ionic conductor for the modification being prepared is added in semiconductive composite material, modified semiconductive composite wood is obtained
Material.
10. preparation method according to claim 8 or claim 9, which is characterized in that carry out surface to modified fast-ionic conductor and change
Property, the surface is modified to refer to adds surface dispersant in modified fast-ionic conductor；The surface dispersant selects hexadecane
Base trimethylammonium bromide, polymethylacrylic acid, polyethyleneimine or isopropyl triisostearoyltitanate；The surface dispersant
Quality accounting in modified semiconductive composite material is not more than 1%.
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