CN107565160A - A kind of polymer dielectric and preparation method thereof and lithium ion battery - Google Patents
A kind of polymer dielectric and preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The present invention relates to field of lithium ion battery, discloses a kind of polymer dielectric and preparation method thereof and lithium ion battery.The polymer dielectric contains polymer, lithium salts and modified inorganic material, and the modified inorganic material is the inorganic material that surface key is connected with organic lithium salt group.Polymer dielectric provided by the invention has very high ionic conductivity.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular it relates to a kind of polymer dielectric and its preparation
Method and lithium ion battery.
Background technology
Lithium ion battery is as a kind of novel energy storage cell because the advantages that capacity is high, energy density is big is considered as
The contenders of electrokinetic cell of future generation, it is recognized as being closest to commercialized battery.Lithium-ion electric
Pond includes positive pole, negative pole and the intermediate electrolyte layer between both positive and negative polarity.
It is presently used for usually containing polymer and lithium salts in the full solid state polymer electrolyte of lithium ion.This
Outside, it is the ionic conductivity of raising polymer dielectric, it will usually inorganic material is introduced in electrolyte system
Material.However, inorganic nano-particle is introduced in the polymer, although electrical conductivity has a certain degree of improve (to lead to
Often there are about an order of magnitude), but because nano-particle is difficult to disperse, is mostly aggregate, it can be caused
Interface interaction unobvious, and improvement of the more nano-particle to ionic conductivity has certain suppression
Effect.For the problem, the common practice taken at present be use silane coupler modified nano-particle with
Improve the dispersiveness of nano-particle.Change for example, CN103066323A discloses a kind of inorganic nano-particle
Property polymer dielectric, the polymer dielectric by containing ethyoxyl ionic compound be grafted it is inorganic
Nano-particle is made with polymer dielectric by being blended, wherein, inorganic nano-particle is in polymer electrolytic
Content in matter is 1-40 weight %.However, the amplitude improved to ionic conductivity using this method is very
It is limited.
The content of the invention
The invention aims to overcome the ionic conductivity of existing polymer dielectric is relatively low to lack
Fall into, and providing a kind of can significantly improve polymer dielectric of ionic conductivity and preparation method thereof and lithium
Ion battery.
Improvement mechanism of the introducing of inorganic material to polymer dielectric electrical conductivity is construed to：As shown in figure 1,
When inorganic material (ball of grey 1/4) is incorporated into polymer (black curve) electrolyte system,
Density regions can be formed in the interface of inorganic material, the feature of polymer in the region shows as gathering
Compound nodeless mesh, segment more " freedom " (glass transition temperature TgIt is relatively low), there is liquid feature (stream
Dynamic property is good)；Further, since the lithium ion (ball) in polymer matrix body phase is deposited with inorganic nano-particle
Interacted in Lewis Acids and Bases, part lithium ion can be caused to be bound in the surface of inorganic nano-particle
(i.e. density regions in figure), carried out compared to the lithium ion in polymer matrix body phase rambling
Migration, the lithium ion in inorganic nano-particle interface can more freely move (TgIt is relatively low), and shorten
Its conducting path, so as to migration for lithium ion in polymer matrix body phase provide privileged way (i.e. soon from
Subchannel), contribute to the migration of lithium ion, and then improve ionic conductivity.However, as described above,
Inorganic nano-particle is introduced in the polymer, although electrical conductivity has a certain degree of improvement, due to receiving
Rice corpuscles is difficult to disperse, is mostly aggregate, can cause its interface interaction unobvious, and more nanometer
Improvement of the particle to ionic conductivity has certain inhibitory action.
The present inventor has found after further investigation, is mixed by inorganic material and polymer and lithium salts
Before conjunction, first the surface of inorganic material is modified using organic lithium salt, on the one hand, nothing can be reduced
The agglomeration of machine material, the dispersiveness of inorganic nanoparticles is improved, on the other hand, inorganic material surface
There is the lithium salts that can more dissociate, so as to be more beneficial for the foundation of the fast ion channel of inorganic material interface,
Transmission and migration of the lithium ion in its interface are more beneficial for, and then significantly improves ionic conductivity.It is based on
This, completes the present invention.
Specifically, the invention provides a kind of polymer dielectric, wherein, the polymer dielectric contains
There are polymer, lithium salts and modified inorganic material, the modified inorganic material is that surface key is connected with organolithium
The inorganic material of salt groups.
Present invention also offers the method for preparing polymer electrolytes, this method is included the polymerization
Thing, lithium salts and modified inorganic material are well mixed.
In addition, present invention also offers a kind of lithium ion battery, the lithium ion battery includes positive pole, negative pole
And electrolyte, wherein, the electrolyte is above-mentioned polymer dielectric.
Polymer dielectric provided by the invention has very high ionic conductivity.
In addition, the present invention, by also found after further investigation, the shape of modified inorganic material is to ionic conductance
Rate also has critically important influence, compared to modified inorganic particles material, modified inorganic club-shaped material or
The interface interaction of modified inorganic filamentary material becomes apparent from, and the improvement to ionic conductivity has more advantage.Therefore,
Correspondingly, a preferred embodiment of the invention, being shaped as the modified inorganic material are bar-shaped
And/or wire, it now can significantly more improve ionic conductivity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing be for providing a further understanding of the present invention, and a part for constitution instruction, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is improvement mechanism of the inorganic material to polymer dielectric electrical conductivity；
Fig. 2 is the specific preparation process of modified inorganic material；
Fig. 3 is the microscopic appearance of the modified inorganic material obtained by embodiment 2；
Fig. 4 is TiO used by embodiment 22The FT-IR of nanometer rods and resulting modified inorganic material
Spectrogram；
Fig. 5 is the polymer dielectric film obtained by embodiment 2；
Fig. 6 is the curve map that ionic conductivity varies with temperature.
Embodiment
The embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, this
A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively
Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and single point
Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding
For specific disclosure herein.
Polymer dielectric provided by the invention contains polymer, lithium salts and modified inorganic material, described
Modified inorganic material is the inorganic material that surface key is connected with organic lithium salt group.
According to polymer dielectric provided by the invention, it is preferable that lithium on the modified inorganic material surface
The density of ion is 1 × 10-6-1×10-3mol/cm2, more preferably 1 × 10-6-5×10-4mol/cm2, most
Preferably 1 × 10-5-1×10-4mol/cm2, so it is more beneficial for the raising of ionic conductivity.
The present invention is not particularly limited to the species of the inorganic material, can be it is existing it is various can
For the inorganic nano-particle of polymer dielectric, the example includes but is not limited to：TiO2、SiO2、Al2O3、
MgO、CaO、BaSO4、CeO2、ZnO、ZrO2And SnO2At least one of.
Term " organic lithium salt group " is the group derived from organic lithium salt, one end of the organic lithium salt
Condensation reaction is carried out with the hydroxyl of inorganic material surface, and the other end then forms the organic lithium salt group.
The organic lithium salt group can be the existing various organic groups containing lithium, it is preferable that described organic
Lithium salts group is organic sulfonic acid lithium salts group.In addition, organic lithium salt corresponding with organic lithium salt group is preferred
For the organic sulfonic acid lithium salts with hydroxyl, it is however preferred to have the organic sulfonic acid lithium salts shown in formula (3)：
In formula (3), a is 1-10 integer, preferably 2-5 integer.Most preferably, it is described to have
Machine lithium salts is trihydroxy silicon substrate propane sulfonic acid lithium.Hydroxyl and inorganic material surface in the organic lithium salt
Hydroxyl carries out condensation reaction, is passed to chemical bond and is fixed on inorganic material surface, so enables to nothing
Machine material surface is bonded with high dissociation degree organic lithium salt group, so as to more effectively establish quickly from
Subchannel is to carry out the transmission of lithium ion and migration.
The present invention is not particularly limited to the source of the modified inorganic material, can be by existing each
Kind method is prepared.According to a kind of embodiment of the present invention, the modified inorganic material passes through
Inorganic material and the organic sulfonic acid with hydroxyl and/or the organic sulfonate with hydroxyl be condensed instead
Should, then condensation reaction products progress lithiumation is obtained.Wherein, relative to the nothing of 100 parts by weight
The dosage of machine material, the organic sulfonic acid with hydroxyl and/or the organic sulfonate with hydroxyl is preferably
0.1-100 parts by weight, more preferably 1-50 parts by weight, most preferably 10-20 parts by weight.When the contracting
It is described to carry when conjunction is reacted simultaneously using the organic sulfonic acid with hydroxyl and the organic sulfonate with hydroxyl
The dosage of the organic sulfonic acid of hydroxyl and/or organic sulfonate with hydroxyl refers to organic sulphur with hydroxyl
The dosage of acid and the dosage sum of the organic sulfonate with hydroxyl；When the condensation reaction only with
When the organic sulfonic acid of hydroxyl or organic sulfonate with hydroxyl, the organic sulfonic acid with hydroxyl and
/ or the dosage of organic sulfonate with hydroxyl refer to the dosage of the organic sulfonic acid with hydroxyl or carry
The dosage of the organic sulfonate of hydroxyl.In addition, the formula such as formula (1) of the organic sulfonic acid with hydroxyl
Shown, the organic sulfonate with hydroxyl obtains for the compound hydrolysis as formula as shown in formula (2)
Arrive；
R1、R2And R3It is each independently C1-C8Straight or branched alkyl, be preferably each independently
C1-C5Straight or branched alkyl；M is K, Na or Li, preferably K or Na；M and n are each
1-10 integer independently is, is preferably each independently 2-5 integer.Most preferably, with hydroxyl
Organic sulfonic acid for trihydroxy silicon substrate propane sulfonic acid (there is the structure shown in formula (1), and 3) n is,
The organic sulfonate with hydroxyl is that 3- trimethyl silicon substrate -1- propanesulfonates (have shown in formula (2)
Structure, and R1、R2And R3It is methyl, M Na, m 3).The purpose of the lithiumation is
In order to which organic sulfonic acid is converted into organic sulfonic acid lithium, its mode be preferably by the condensation reaction products with
LiOH is reacted.During the lithiumation, relative to carrying hydroxyl described in 100 parts by weight
Organic sulfonic acid and organic sulfonate with hydroxyl total dosage, the dosage of the LiOH is preferably
0.1-20 parts by weight, more preferably 0.1-10 parts by weight, most preferably 1-8 parts by weight.
The present invention is not particularly limited to the condition of the condensation reaction and lithiumation.For example, the condensation
It is 20-60 DEG C that the condition of reaction, which can include reaction temperature, reaction time 5-48h.The lithiation
Condition can include reaction temperature be 20-80 DEG C, reaction time 8-60h.In addition, the condensation is anti-
It should generally be carried out in the presence of the solvent with the process of lithiumation, the species and dosage of the solvent can be
The conventional selection of this area, this those skilled in the art can be known, therefore not to repeat here.
The present invention is not particularly limited to the shape of the modified inorganic material, can be graininess, rod
Shape, wire etc., preferably bar-shaped and/or wire.The present inventor by being found after further investigation,
When the modified inorganic material is bar-shaped and/or wire, the raising of its electrical conductivity is more beneficial for.Term " rod
Shape " refers to that draw ratio k is 5:1≤k ＜ 20:1.Term " wire " refers to that draw ratio k is 20:1≤k
≤100:1。
Fig. 2 is with TiO2Nanometer rods are the preparation process of the modified inorganic material to be carried out exemplified by raw material
It is described in detail.Specifically, first by TiO2Nanometer rods and trihydroxy silicon substrate propane sulfonic acid (THSPSA)
Reacted, TiO2Hydroxyl in nanometer rods is condensed with the hydroxyl on trihydroxy silicon substrate propane sulfonic acid,
Trihydroxy silicon substrate propane sulfonic acid key fixed is set to be scheduled on TiO2In nanometer rods, LiOH is subsequently added into so that TiO2
The sulfonic acid group of nanorod surfaces is converted into Sulfonic Lithium group, obtains the TiO of surface richness lithium2Nanometer rods.
The present invention is not particularly limited to the content of each material in the polymer dielectric, it is preferable that
Relative to the polymer of 100 parts by weight, the content of the lithium salts is 1-100 parts by weight, described to change
The content of property inorganic material is 1-50 parts by weight；It is highly preferred that relative to the described poly- of 100 parts by weight
Compound, the content of the lithium salts is 5-50 parts by weight, and the content of the modified inorganic material is 5-30 weights
Measure part；Most preferably, relative to the polymer of 100 parts by weight, the content of the lithium salts is 8-20
Parts by weight, the content of the modified inorganic material is 8-15 parts by weight.Now the content of the lithium salts is not
Include the content of modified inorganic material surface lithium, only refer in the polymer dielectric in free shape
The content of the lithium salts of state.
The present invention is not particularly limited to the species of the polymer and lithium salts, can be the normal of this area
Rule selection.For example, the polymer can be selected from polyethylene glycol oxide (PEO), poly-methyl methacrylate
At least one of ester, polyacrylonitrile, PPOX and poly-phosphine piperazine, preferably polyethylene glycol oxide, gather
At least one of propylene oxide and polymethyl methacrylate.The lithium salts can be selected from LiClO4、
LiPF6、LiAsF6、LiBF4、LiCF3SO3And C2F6LiNO4S2At least one of, it is preferably
C2F6LiNO4S2、LiPF6And LiBF4At least one of.
The method for preparing polymer electrolytes provided by the invention include by the polymer, lithium salts with
And modified inorganic material is well mixed.Wherein, the mixing is preferably carried out in the presence of the solvent, described
Solvent is such as can be water, alcohol.As long as the condition of the mixing enables to above-mentioned each material mixing equal
It is even, this those skilled in the art can be known, therefore not to repeat here.
In addition, the polymer dielectric is used for lithium ion battery in order to be more convenient for, it is preferable that described
Method for preparing polymer electrolytes also includes pouring into the material that above-mentioned raw materials obtain after well mixed
The step of film, concrete operations are known to the skilled person, and therefore not to repeat here.
Lithium ion battery provided by the invention includes positive pole, negative pole and electrolyte, wherein, the electrolyte
For above-mentioned polymer dielectric.
Theing improvement is that for lithium ion battery provided by the invention employs a kind of new electrolyte, and just
The species and positive pole of pole and negative pole, the position relationship between negative pole and electrolyte can be with prior arts
It is identical, this those skilled in the art can be known, therefore not to repeat here.
The present invention will be described in detail by way of examples below.
In following examples, lithium ion density=(4 × weight-loss ratio × inorganic material dosage) ÷ (1.5 ×
The molecular weight of organic sulfonic acid), wherein, 4 be titanium dioxide bulk density, and 1.5 be titanium dioxide true reactor
Product density, weight-loss ratio be modified inorganic material before and after pyrolysis the rate of change of quality and its use thermogravimetry
It is measured, the unit of inorganic material dosage is g.
Embodiment 1
The embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
At 25 DEG C, by 0.3g TiO2Nano particle (average grain diameter 25nm) is in N, N- diformazans
24h is dispersed with stirring in yl acetamide (DMAc, 5g), adds 3- trihydroxy silicon substrate propane sulfonic acid water
Solution 0.5g (solid content is 10 weight %) continues after stirring 24h, and it is water-soluble to be subsequently added into 0.2g LiOH
Liquid (concentration is 2.5 weight %) stirring reaction 48h, after finally filtering out solvent, is washed with deionized water
Three times, the nano material of organic sulfonic acid lithium salts modification is obtained, afterwards by the modified Nano material at 60 DEG C
Baking 24h obtains modified inorganic material C1, the density of lithium ion is 8 on its surface to remove moisture
×10-5mol/cm2。
0.025g modified inorganic materials C1 is added to (dense containing polyethylene glycol oxide PEO aqueous solution 5g
The number-average molecular weight spent for 5 weight %, PEO is 1000000g/mol, similarly hereinafter) and 0.02g
C2F6LiNO4S2(weight compares PEO：Lithium salts=12.5：1) in the aqueous solution, poured into a mould after stirring 24h
Film forming, obtains polymer dielectric film M1, and thickness is 80 μm.
Embodiment 2
The embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
At 25 DEG C, by 0.3g TiO2(average length 800nm, average diameter are nanometer rods
24h 100nm) is dispersed with stirring in DMA (DMAc, 5g), adds 3- tri-
Hydroxyl silicon substrate propane sulfonic acid aqueous solution 0.5g (solid content is 10 weight %) continues after stirring 24h, connects
The addition 0.2g LiOH aqueous solution (concentration is 2.5 weight %) stirring reaction 48h, is finally filtered out molten
After agent, the nano material for three times, obtaining the modification of organic sulfonic acid lithium is washed with deionized water, is afterwards modified this
Nano material toasts 24h to remove moisture at 60 DEG C, modified inorganic material C2 is obtained, on its surface
The density of lithium ion is 8 × 10-5mol/cm2.Using SEM (SEM, JEOL,
JSM-7600FE modified inorganic material C2 microscopic appearance) is observed, as a result as shown in figure 3, from figure
3 as can be seen that modified nanometer rods are not reunited, and have preferably dispersiveness.In addition, using FT-IR
To TiO before modified2Nanometer rods and modified inorganic material C2 are characterized, as a result as shown in figure 4, its
In, a is TiO before modified2The infrared spectrum of nanometer rods, b are modified inorganic material C2 INFRARED SPECTRUM
Figure.It can be seen that after modified from Fig. 4 result, it can be seen that TiO2Surface functional group changes,
1046cm-1For Si-O-Si vibration peak, 1217cm-1For-SO3H vibration peak, 2791cm-1For-CH2
Stretching vibration peak, illustrate that key is connected to TiO to 3- trihydroxy silicon substrates propane sulfonic acid2Nanorod surfaces.
0.025g modified inorganic materials C2 is added to (dense containing polyoxyethylene PEO aqueous solution 5g
Spend for 5 weight %) and 0.02g C2F6LiNO4S2(weight compares PEO：Lithium salts=12.5：1) water-soluble
In liquid, film forming is poured into a mould after stirring 24h, obtains polymer dielectric film M2, thickness is 80 μm, and it shines
Piece as shown in figure 5, from fig. 5, it can be seen that the full solid state polymer electrolyte film film forming poured into a mould compared with
It is good, there is some strength.
Embodiment 3
The embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
At 25 DEG C, by 0.3g TiO2(average length 2000nm, average diameter are nano wire
24h 20nm) is dispersed with stirring in DMA (DMAc, 5g), adds the hydroxyls of 3- tri-
Base silicon substrate propane sulfonic acid aqueous solution 0.5g (solid content is 10 weight %) continues after stirring 24h, then
The 0.2g LiOH aqueous solution (concentration is 2.5 weight %) stirring reaction 48h is added, finally filters out solvent
Afterwards, the nano material for three times, obtaining the modification of organic sulfonic acid lithium is washed with deionized water, afterwards receives the modification
Rice material toasts 48h to remove moisture at 60 DEG C, obtains modified inorganic material C3, lithium on its surface
The density of ion is 8 × 10-5mol/cm2。
0.025g modified inorganic materials C3 is added to (dense containing polyoxyethylene PEO aqueous solution 5g
Spend for 5 weight %) and 0.02g C2F6LiNO4S2(weight compares PEO：Lithium salts=12.5：1) water-soluble
In liquid, film forming is poured into a mould after stirring 24h, obtains polymer dielectric film M3, thickness is 80 μm.
Embodiment 4
The embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
Method according to embodiment 2 prepares modified inorganic material and polymer dielectric, unlike, will
3- trihydroxy silicon substrate propane sulfonic acid usage amounts are reduced to 1/4, obtain modified inorganic material C4 and electrostrictive polymer
Plasma membrane M4 is solved, wherein, the density of lithium ion is 2 × 10 on modified inorganic material C4 surfaces-6mol/cm2,
Polymer dielectric film M4 thickness is 80 μm.
Embodiment 5
The embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
Method according to embodiment 2 prepares modified inorganic material and polymer dielectric, unlike, will
3- trihydroxy silicon substrate propane sulfonic acids amount reduces one times, obtains modified inorganic material C5 and polymer dielectric
Film M5, wherein, the density of lithium ion is 4 × 10 on modified inorganic material C5 surfaces-5mol/cm2, gather
Polymer electrolyte membrane M5 thickness is 80 μm.
Comparative example 1
The comparative example is used to illustrate polymer dielectric of reference and preparation method thereof.
At 25 DEG C, by 0.3g TiO2Nano particle (average grain diameter 25nm) is in N, N- diformazans
24h is dispersed with stirring in yl acetamide (DMAc, 5g), adds the ethoxy of coupling agent 3- aminopropyls three
Base silane aqueous solution 1.4g (solid content is 35 weight %) continues to stir 24h, after finally filtering out solvent,
It is washed with deionized water and three times, obtains through silane coupler modified nano material, afterwards by the nano material
24h is toasted at 60 DEG C to remove moisture, obtains reference modified inorganic material DC1.
Method according to embodiment 1 prepares polymer dielectric film, unlike, by modified inorganic material
C1 is substituted with the reference modified inorganic material DC1 of identical weight part, obtains reference polymer dielectric film
DM1, its thickness are 80 μm.
Comparative example 2
The comparative example is used to illustrate polymer dielectric of reference and preparation method thereof.
Method according to embodiment 1 prepares polymer dielectric, unlike, TiO2Nano particle without
Modified be directly used in prepares polymer dielectric film, i.e. by modified inorganic material C1 with identical weight part
TiO2Particle substitutes, and obtains reference polymer dielectric film DM2, and its thickness is 80 μm.
Test case
Test case is used for the test for illustrating polymer dielectric film ionic conductivity.
The ionic conductivity test of polymer dielectric is that polymer dielectric film is clipped in into two specification phases
Between same stainless steel (SS) electrode, and seal, form SS/SPEs/SS batteries, its is effective
Area is 2cm2, thickness is 100 μm, tests the electrochemical AC impedance of SS/SPE/SS structure batteries
Spectrogram (EIS), test frequency is from 1Hz to 1MHz.Acquired results are as shown in table 1, wherein, test
Temperature is 70 DEG C.In addition, non-modified TiO2Nano particle, modified inorganic material C1-C2, ginseng
Ionic conductivity than modified inorganic material DC1 varies with temperature curve map as shown in fig. 6, from Fig. 6
Result can be seen that the ionic conductivity highest of the polymer dielectric containing modified inorganic material C2,
Secondly it is the polymer dielectric containing modified inorganic material C1, minimum is to contain reference modified inorganic
Material DC1 and unmodified inorganic nanoparticles polymer dielectric.
Table 1
| Numbering | Polymer dielectric film | Ionic conductivity (S/cm, 60 DEG C) |
| Embodiment 1 | M1 | 2.5×10-5 |
| Embodiment 2 | M2 | 5.2×10-4 |
| Embodiment 3 | M3 | 4.9×10-4 |
| Embodiment 4 | M4 | 1.3×10-4 |
| Embodiment 5 | M5 | 2.5×10-4 |
| Comparative example 1 | DM1 | 6.4×10-6 |
| Comparative example 2 | DM2 | 2.6×10-6 |
As can be seen from the above results, polymer dielectric provided by the invention has very high ion-conductance
Conductance.The situation in other conditions all same is can be seen that from embodiment 1 and embodiment 2-3 contrast
Under (density of lithium ion is identical), be shaped as bar-shaped and/or wire when the modified inorganic nano material
When, it can significantly more improve ionic conductivity.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to the technical side of the present invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Sign, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention no longer separately illustrate to various combinations of possible ways.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (12)
- A kind of 1. polymer dielectric, it is characterised in that the polymer dielectric contain polymer, Lithium salts and modified inorganic material, the modified inorganic material are the nothing that surface key is connected with organic lithium salt group Machine material.
- 2. polymer dielectric according to claim 1, wherein, the modified inorganic material table The density of lithium ion is 1 × 10 on face-6-1×10-3mol/cm2, preferably 1 × 10-6-5× 10-4mol/cm2, more preferably 1 × 10-5-1×10-4mol/cm2。
- 3. polymer dielectric according to claim 1, wherein, the inorganic material is TiO2、 SiO2、Al2O3、MgO、CaO、BaSO4、CeO2、ZnO、ZrO2And SnO2In at least one Kind.
- 4. according to the polymer dielectric described in any one in claim 1-3, wherein, it is described to have Machine lithium salts group is organic sulfonic acid lithium salts group.
- 5. polymer dielectric according to claim 4, wherein, the modified inorganic material leads to Cross and be condensed inorganic material and the organic sulfonic acid with hydroxyl and/or the organic sulfonate with hydroxyl Reaction, then condensation reaction products progress lithiumation is obtained.
- 6. polymer dielectric according to claim 5, wherein, relative to 100 parts by weight The dosage of the inorganic material, the organic sulfonic acid with hydroxyl and/or the organic sulfonate with hydroxyl For 0.1-100 parts by weight；Shown in the formula such as formula (1) of the organic sulfonic acid with hydroxyl, the band The organic sulfonate for having hydroxyl obtains for the compound hydrolysis as formula as shown in formula (2)；R1、R2And R3It is each independently C1-C8Straight or branched alkyl, M K, Na or Li, M and n is each independently 1-10 integer.
- 7. polymer dielectric according to claim 5, wherein, the mode of the lithiumation is will The condensation reaction products are reacted with LiOH；Relative to carrying hydroxyl described in 100 parts by weight Total dosage of organic sulfonic acid and organic sulfonate with hydroxyl, the dosage of the LiOH is 0.1-20 weights Measure part.
- 8. according to the polymer dielectric described in any one in claim 1-3, wherein, it is described to change Property inorganic material is shaped as bar-shaped and/or wire.
- 9. according to the polymer dielectric described in any one in claim 1-3, wherein, described In polymer dielectric, relative to the polymer of 100 parts by weight, the content of the lithium salts is 1-100 Parts by weight, the content of the modified inorganic material is 1-50 parts by weight.
- 10. according to the polymer dielectric described in any one in claim 1-3, wherein, it is described poly- Compound is selected from polyethylene glycol oxide, polymethyl methacrylate, polyacrylonitrile, PPOX and poly-phosphine piperazine At least one of, the lithium salts is selected from LiClO4、LiPF6、LiAsF6、LiBF4、LiCF3SO3With C2F6LiNO4S2At least one of.
- 11. the method for preparing polymer electrolytes in claim 1-10 described in any one, the party Method includes the polymer, lithium salts and modified inorganic material being well mixed.
- 12. a kind of lithium ion battery, the lithium ion battery includes positive pole, negative pole and electrolyte, its feature It is, the electrolyte is the polymer dielectric described in any one in claim 1-10.
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| CN110416600A (en) * | 2018-04-28 | 2019-11-05 | 上海汽车集团股份有限公司 | A kind of polymer dielectric film and solid state battery |
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