CN107666010A - A kind of lithium ion battery solid electrolyte, its preparation method and lithium ion battery - Google Patents
A kind of lithium ion battery solid electrolyte, its preparation method and lithium ion battery Download PDFInfo
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- CN107666010A CN107666010A CN201610613034.7A CN201610613034A CN107666010A CN 107666010 A CN107666010 A CN 107666010A CN 201610613034 A CN201610613034 A CN 201610613034A CN 107666010 A CN107666010 A CN 107666010A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention proposes a kind of lithium ion battery solid electrolyte, its preparation method, and lithium ion battery, the lithium ion battery solid electrolyte, including inner nuclear material and the sheathing material for being coated on the inner nuclear material outer surface；The inner nuclear material includes Li1+xMxTi2‑x(PO4)3, wherein, M is selected from least one of Al, La, Cr, Ga, Y or In, 0.05 ￡ x£0.4, the sheathing material includes Li0.6+ yB0.8SiyP1‑yO4, wherein, 0.01 ￡ y£0.5。Li0.6+ yB0.8SiyP1‑yO4Sufficiently the face of progress contacts sheathing material with inner nuclear material, hence it is evident that reduces the ability of inner nuclear material intercrystalline resistance, and it has relatively low electronic conductivity, and complete fine and close electronic shield layer is formed on inner nuclear material surface, solves Ti well4+It is reduced to Ti3+The problem of.Obtained solid electrolyte has wide electrochemical window（Electrochemical window ＞ 5V）, higher ionic conductivity and low electronic conductivity.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly to a kind of lithium ion battery solid electrolyte, its preparation method,
And the lithium ion battery using the solid electrolyte.
Background technology
Lithium ion battery is commonly used to consumer electronics because efficiency density is high, fills the advantages that performance is good, service wear is small again
Field and electric automobile.High energy efficiency, highdensity chemical cell are realized usually by organic liquid electrolytes at present, and liquid
There is the problems such as volatile, inflammable and leakage is corroded, it is necessary to add multiple safety protection measure to battery in electrolyte so that large-scale
Battery system is complex and costly.Although gel polymer electrolyte combines the high security and liquid electrolyte of solid electrolyte
The high conductivity and high rate performance of matter, solve the problems, such as lithium ion battery security to a certain extent, but still use liquid
State organic solvent is as plasticizer, it is impossible to solves safety issue from source.It is fast that lithium ion inorganic solid electrolyte is also known as lithium
Ion conductor (Super ionic conductor), this kind of material have higher Li+Electrical conductivity and Li+Transport number, conductance
Activation energy is low, and resistance to elevated temperatures is good, has good application prospect in the large-sized power lithium ion battery of high-energy-density.With lithium from
Sub- inorganic solid electrolyte replaces organic liquid electrolytes, the shortcomings that can overcoming internal short-circuit of battery and leakage, improve lithium from
The security that sub- battery uses.Thus, it is lithium ion battery material research field all the time to lithium ion solid state electrolysis Quality Research
One of hot issue.
The research of current lithium ion inorganic solid electrolyte is concentrated mainly on LISICON（Zinc germanate lithium）Structure,
NASICON（Na Superionic CONductor, sodium superionic conductors）Structure, perovskite structure, class garnet structure
Crystalline state lithium ion solid electrolyte and oxide, sulfide, Oxide and sulfide mixed type glassy state lithium ion solid-state electricity
Xie Zhi, not only solve safety issue from source, and can work in high temperature environments, above-mentioned advantage is other electrolysis
Not available for plastidome.Especially there is the Li of NASICON structures1.3Al0.3Ti1.7(PO4)3（LATP）Being can be to pass at a high speed
The lithium ion inorganic solid electrolyte of lithium ion is led, therefore researchers enter to be about to the compound and are used for solid electrolyte
The exploitation of all solid state secondary battery.
LATP conductivity at room temperature conductance can reach 10-4S/cm, with commercialized liquid electrolyte at present
Electrical conductivity be closer to.But LATP electrochemical window is narrow, only 2.5V, it is strongly limit in solid state lithium battery
In practical application.There is the solid lithium-ion electrolyte for disclosing a kind of NASICON types in the prior art, the solid electrolyte is adopted
Collaboration doping is carried out to LATP with zinc, silicon and sulphion.Although above-mentioned technical proposal can be more than LATP lithium ion conductivity
10-4S/cm, but the electrochemical window of the LATP after doping vario-property is still narrower, and the possibility of battery short circuit, security be present
Can be low.
The content of the invention
The present invention is in order to solve Li of the prior art1.3Al0.3Ti1.7(PO4)3Class solid electrolyte electrochemical window is narrow
Technical problem, there is provided a kind of lithium ion battery solid electrolyte, its preparation method, and lithium ion battery.
First purpose of the present invention is to provide a kind of lithium ion battery solid electrolyte, including inner nuclear material and is coated on
The sheathing material of the inner nuclear material outer surface；The inner nuclear material includes Li1+xMxTi2-x(PO4)3, wherein, M be selected from Al, La,
At least one of Cr, Ga, Y or In, 0.05 ￡ x£0.4；, the sheathing material includes Li0.6+yB0.8SiyP1-yO4, wherein,
0.01£y£0.5。
Second object of the present invention is to provide the preparation method of above-mentioned solid electrolyte, and step includes：
S1, inner nuclear material is obtained, the inner nuclear material includes Li1+xMxTi2-x(PO4)3, wherein, M be selected from Al, La, Cr, Ga, Y or
At least one of In, 0.05 ￡ x£0.4；
S2, the inner nuclear material mixed with the solution containing shell lithium source, shell phosphate, silicon source and boron source, adjust pH value
For 8 ~ 11, dry precursor material；
S3, the precursor material calcined, the solid electrolyte is obtained after cooling.
Third object of the present invention is to provide a kind of lithium ion battery, including positive pole, negative pole and is arranged at the positive pole
Solid electrolyte between negative pole；Wherein, the solid electrolyte is above-mentioned lithium ion battery solid electrolyte.
The present inventor is by largely testing discovery, although the Li of NASICON structures1.3Al0.3Ti1.7(PO4)3
（LATP）Conductivity at room temperature conductance can reach 10-4S/cm, with the conductance of commercialized liquid electrolyte at present
Rate is closer to.But because it contains the titanium ion easily to appraise at the current rate, when LATP contacts with the negative material of low potential, Ti4+Can quilt
It is reduced to Ti3+, electronic conductance is produced, causes its electrochemical window narrow.Ion doping is carried out to LATP in the prior art, although
LATP conductivity at room temperature is improved to a certain extent, but can not improve what such material was reduced under low potential
Problem, when it is used as the solid electrolyte of lithium ion battery, it is difficult to avoid causing battery short due to the generation of electronic conductance
Road.
The problem of for above-mentioned discovery, the present invention provides a kind of lithium ion solid electrolyte, high using ionic conductivity
Li1+xMxTi2-x(PO4)3As inner nuclear material, Li is coated in the outer surface of inner nuclear material0.6+yB0.8SiyP1-yO4Sheathing material, outside
There is Si in shell material4+, it can substitute P5+It is incorporated to Li0.6B0.8PO4Lattice, change the lattice of material, the crystallinity drop of material
Low, material surface physicochemical properties change, so as to which sufficiently the face of progress contacts with inner nuclear material, hence it is evident that it is brilliant to reduce inner nuclear material
The ability of intergranular resistance, and it has relatively low electronic conductivity, and complete fine and close electrical screen is formed on inner nuclear material surface
Layer is covered, external electrical is shielded and can not be contacted with inner nuclear material by sheathing material, solves Ti well4+It is reduced to Ti3+
The problem of.The sheathing material also has high ionic conductivity simultaneously, does not interfere with the conduction of lithium ion.Therefore above-mentioned solid-state electricity
Solution matter has wide electrochemical window（Electrochemical window ＞ 5V）, higher ionic conductivity and low electronic conductivity.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining
The present invention, it is not intended to limit the present invention.
The invention provides a kind of lithium ion battery solid electrolyte, and it includes inner nuclear material and is coated on the kernel material
Expect the sheathing material of outer surface；The inner nuclear material includes Li1+xMxTi2-x(PO4)3, wherein, M be selected from Al, La, Cr, Ga, Y or
At least one of In, 0.05 ￡ x£0.4；, the sheathing material includes Li0.6+yB0.8SiyP1-yO4, wherein, 0.01 ￡ y£0.5。
It is preferred that the ionic conductivity of sheathing material is 10-6More than S/cm, electronic conductivity are less than 10-10S/cm, further
Ensure the shield effectiveness of electronic shield layer and the ionic conductivity of solid electrolyte, further preferably, the ion-conductance of sheathing material
Conductance is 10-6~10-5S/cm。
Specifically, it is preferable that sheathing material is selected from Li0.65B0.8Si0.05P0.95O4、Li0.7B0.8Si0.1P0.9O4、
Li0.8B0.8Si0.2P0.8O4、Li0.9B0.8Si0.3P0.7O4、LiB0.8Si0.4P0.6O4Or Li1.1B0.8Si0.5P0.5O4In at least one
Kind, there is preferably synergy, and have relatively low electronic conductivity and higher ionic conductivity with inner nuclear material.
It is preferred that the thickness of sheathing material is 10 ~ 30nm.
According to lithium ion battery solid electrolyte provided by the present invention, to realize good covered effect, avoid simultaneously
The electrical conductivity of excessive influence solid electrolyte, under preferable case, on the basis of the gross weight of the solid electrolyte, the shell
The content of material is 0.5-10wt%.
In the present invention, inner nuclear material uses the Li of conventional NASICON structures1+xMxTi2-x(PO4)3Material.Meet above-mentioned
The inner nuclear material of condition can use various existing known materials, and under preferable case, the inner nuclear material is selected from Li1.1Y0.1Ti1.9
(PO4)3、Li1.3Y0.3Ti1.7(PO4)3、Li1.4Y0.4Ti1.6(PO4)3、Li1.1Al0.1Ti1.9(PO4)3、Li1.3Al0.3Ti1.7
(PO4)3、Li1.05La0.05Ti1.95(PO4)3、Li1.1Cr0.1Ti1.9(PO4)3、Li1.1Ga0.1Ti1.9(PO4)3Or Li1.1In0.1Ti1.9
(PO4)3At least one of, electrical conductivity is higher, and chemical property is stable, is not reacted with air and moisture.
For above-mentioned inner nuclear material, its average grain diameter can be in interior variation in a big way, in the present invention, under preferable case, institute
The average grain diameter for stating inner nuclear material is 0.5 ~ 10 μm.
Invention also provides the preparation method of above-mentioned solid electrolyte, its step includes：
S1, inner nuclear material is obtained, the inner nuclear material includes Li1+xMxTi2-x(PO4)3, wherein, M be selected from Al, La, Cr, Ga, Y or
At least one of In, 0.05 ￡ x£0.4；
S2, the inner nuclear material mixed with the solution containing shell lithium source, shell phosphate, silicon source and boron source, adjust pH value
For 8 ~ 11, dry precursor material.Solution used in regulation pH value is generally ammoniacal liquor, solution is coated on inner nuclear material in gel
Outer surface, precursor material is then obtained after drying.By the solution containing shell lithium source, shell phosphate, silicon source and boron source with
When inner nuclear material mixes, the relative amount of the two can be under interior variation in a big way, preferable case, to ensure the solid-state electricity formed
The content for solving sheathing material described in matter is that 0.5 ~ 10wt% is preferable, and the thickness of the sheathing material of formation is 10 ~ 30nm.
S3, the precursor material calcined, the solid electrolyte is obtained after cooling.By above-mentioned calcining, by before
In body material, the gel transition for being coated on inner nuclear material outer surface is that chemical formula is Li0.6+yB0.8SiyP1-yO4Solid outer shell material
Material, wherein, 0.01 ￡ y£0.5。
It is preferred that the temperature of calcining is 900 ~ 1200 DEG C, the time is 8 ~ 24h.Under preferable case, the method for calcining is specially：
900 ~ 1200 DEG C are warming up to 2 ~ 10 DEG C/min programming rate and are incubated 8 ~ 24h.
,, can be to it before being calcined to precursor material in above-mentioned steps S3 according to final concrete application as existing
It is pressed, forms required concrete shape, such as can is the formed body of the arbitrary shapes such as thin slice, cylinder and thickness,
Specifically depending on the design requirement of solid electrolyte, then calcined again.
In above-mentioned steps S1, the Li as inner nuclear material1+xMxTi2-x(PO4)3For material of the prior art, it is preferable that interior
Nuclear material is selected from Li1.1Y0.1Ti1.9(PO4)3、Li1.3Y0.3Ti1.7(PO4)3、Li1.4Y0.4Ti1.6(PO4)3、Li1.1Al0.1Ti1.9
(PO4)3、Li1.3Al0.3Ti1.7(PO4)3、Li1.05La0.05Ti1.95(PO4)3、Li1.1Cr0.1Ti1.9(PO4)3、Li1.1Ga0.1Ti1.9
(PO4)3Or Li1.1In0.1Ti1.9(PO4)3At least one of；It is preferred that the average grain diameter of inner nuclear material is 0.5 ~ 10 μm.
Its preparation method is known, preferably can also can with the following method be prepared with purchased in market, kernel is obtained in step S1
The method of material includes, and titanium source, metal M sources, kernel lithium source, kernel phosphate are mixed and tentatively calcined, and obtains described
Inner nuclear material；By element Li, metal M, Ti, P molar content in terms of, the kernel lithium source, metal M sources, titanium source, kernel phosphate
The ratio between content be（1+x）~1.2（1+x）：x：（2-x）：3, by the excessive addition kernel lithium source of appropriateness, high temperature can be replenished
The loss of lithium ion in heating process, while other accessory substances will not be produced.
Specifically, above-mentioned titanium source can use conventional titanium-containing compound, it is preferable that titanium source is selected from TiO2。
In above-mentioned chemical formula, M is selected from least one of Al, La, Cr, Ga, Y or In.Specifically, metal M sources can be selected
From the respective compound of above-mentioned various metals, it is preferable that the metal M sources may be selected from Al2O3、Y2O3、Ga2O3、La2O3、Cr2O3、
In2O3In one or more.
Kernel lithium source can use various lithium-containing compounds commonly used in the art, it is preferable that the kernel lithium source may be selected from carbonic acid
One or more in lithium, lithium hydroxide, a hydronium(ion) lithia, lithium nitrate, lithium acetate.
It is preferred that kernel phosphate may be selected from NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、H3PO4In one or more.
The method that above-mentioned kernel lithium source, metal M sources, titanium source, kernel phosphate are mixed can use conventional ball milling work
Skill, after ball milling, you can tentatively calcined, to obtain chemical formula as Li1+xMxTi2-x(PO4)3Inner nuclear material, wherein, M is selected from
At least one of Al, La, Cr, Ga, Y or In, 0.05 ￡ x£0.4。
, according to the invention it is preferred to which above-mentioned precalcined temperature is 750 ~ 950 DEG C, the time is 4 ~ 16h.
Under preferable case, by the control to ball milling and preliminary calcine technology, the average grain of the inner nuclear material can be made
Footpath is 0.5 ~ 10 μm.
According to the present invention, in above-mentioned steps S2, it is preferable that according to the composition of the sheathing material of required acquisition, by shell lithium source,
Shell phosphate, silicon source and the boron source obtained solution containing shell lithium source, shell phosphate, silicon source and boron source soluble in water, it is excellent
Choosing, in terms of element molar content, element Li in the solution containing shell lithium source, shell phosphate, silicon source and boron source：B : Si：P
For 0.65 ~ 1.1：0.8：（y）：（1-y）, wherein, 0.01 ￡ y£0.5。
For above-mentioned shell lithium source, shell phosphate, silicon source and boron source, various things commonly used in the prior art can be used
Matter, it is preferable that the boron source is selected from H3BO3、B2O3、LiBO2, one or more in triethyl borate；The shell lithium source is selected from
One or more in lithium carbonate, lithium hydroxide, a hydronium(ion) lithia, lithium nitrate, lithium acetate；The shell phosphate is selected from
NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、H3PO4In one or more；The silicon source is tetraethyl orthosilicate.Wherein, shell
Lithium source, shell phosphate and kernel lithium source, kernel phosphate can be the same or different.
It should be understood that according to the shell lithium source of use, shell phosphate, silicon source and the specific material of boron source and addition
Difference, the specific chemical formula of the sheathing material of acquisition is also different, specifically, sheathing material can be selected from
Li0.65B0.8Si0.05P0.95O4、Li0.7B0.8Si0.1P0.9O4、Li0.8B0.8Si0.2P0.8O4、Li0.9B0.8Si0.3P0.7O4、
LiB0.8Si0.4P0.6O4Or Li1.1B0.8Si0.5P0.5O4At least one of.
In addition, the present invention additionally provides a kind of lithium ion battery simultaneously, including positive pole, negative pole and be arranged at the positive pole and
Solid electrolyte between negative pole；The solid electrolyte is foregoing lithium ion battery solid electrolyte.
In above-mentioned lithium ion battery, positive pole and negative pole can use various materials and structure commonly used in this field, for example,
The positive electrode includes at least one of cobalt acid lithium, LiMn2O4, LiFePO4 or nickel-cobalt-manganese ternary material；The negative pole material
Material includes at least one of lithium metal, graphite, carbonaceous mesophase spherules, mesophase carbon fiber, soft carbon, hard carbon, lithium titanate.
Above-mentioned lithium ion battery can be also prepared by the method for routine, for example, by solid electrolyte, positive pole and negative pole
All-solid lithium-ion battery is assembled into together.
The present invention is further detailed below by way of specific embodiment.
Embodiment 1
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 2.10gLi is weighed respectively2CO3Powder, 0.26g Al2O3Powder, 7.86g TiO2Powder and 17.86g
NH4H2PO4, ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 800 DEG C of preliminary calcinings
6h, it is Li that chemical formula is obtained after cooling1.1Al0.1Ti1.9(PO4)3Inner nuclear material powder.Its average grain diameter is 5 μm.
3rd, 0.07gLiOH, 0.18g H are weighed3BO3、0.34g NH4H2PO4Deionization is scattered in 0.15g tetraethyl orthosilicates
The aqueous solution is formed in water, adds the Li of the above-mentioned preparations of 20g1.1Al0.1Ti1.9(PO4)3Inner nuclear material powder, strong stirring is uniform, and
It is 11 with the pH value of 2mol/L ammoniacal liquor regulation systems, forms homogeneous gel and be coated on Li1.1Al0.1Ti1.9(PO4)3Inner nuclear material powder
On body particle, the precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1000 DEG C are warming up to 2 DEG C/min programming rate and is incubated 24 hours, and required solid electrolyte sheet is just obtained after cooling
A1, obtained sheathing material are Li0.8B0.8Si0.2P0.8O4, solid electrolyte gross mass 2wt% is accounted for, utilizes electron microscope observation
The thickness of sheathing material is 30nm.
Embodiment 2
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
Solid electrolyte sheet A2 is prepared using method and step same as Example 1.Different is to weigh
2.07gLi2CO3Powder, 0.57g Y2O3Powder, 7.73g TiO2Powder and 17.58g NH4H2PO4Li is made1.1Y0.1Ti1.9
(PO4)3Inner nuclear material powder, its average grain diameter are 5 μm.The Li of the above-mentioned preparations of 20g is added in the aqueous solution1.1Y0.1Ti1.9(PO4)3
Inner nuclear material powder, the thickness of the sheathing material of formation is 25nm.
Embodiment 3
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
Solid electrolyte sheet A3 is prepared using method and step same as Example 1.Different is to weigh
3.12gLi2CO3Powder, 0.72g Ga2O3Powder, 11.60g TiO2Powder and 26.50g NH4H2PO4It is made
Li1.1Ga0.1Ti1.9(PO4)3Inner nuclear material powder, the 500rpm ball millings 16h in planetary ball mill, it is 2 μ to make its average grain diameter
m.The Li of the above-mentioned preparations of 30g is added in the aqueous solution1.1Ga0.1Ti1.9(PO4)3Inner nuclear material powder, the thickness of the sheathing material of formation
For 10nm.
Embodiment 4
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 2.50gLi is weighed respectively2CO3Powder, 0.8g Al2O3Powder, 7.08g TiO2Powder and 18g NH4H2PO4,
Ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 850 DEG C of preliminary calcinings
12h, Li is obtained after cooling1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder.Its average grain diameter is 2 μm.
3rd, 0.17gLiOH, 0.91g H are weighed3BO3、0.85g NH4H2PO4Deionization is scattered in 0.37g tetraethyl orthosilicates
The aqueous solution is formed in water, adds the Li of the above-mentioned preparations of 20g1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder, strong stirring is uniform, and
It is 10 with the pH value of 2mol/L ammoniacal liquor regulation systems, forms homogeneous gel and be coated on Li1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder
On body particle, the precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1100 DEG C are warming up to 2 DEG C/min programming rate and is incubated 20 hours, and required solid electrolyte sheet is just obtained after cooling
A4, obtained sheathing material are Li0.8B0.8Si0.2P0.8O4, solid electrolyte gross mass 5wt% is accounted for, the thickness of sheathing material is
20nm。
Embodiment 5
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 1.88gLi is weighed respectively2CO3Powder, 0.6g Al2O3Powder, 5.31g TiO2Powder and 13.5g
NH4H2PO4, ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 850 DEG C of preliminary calcinings
12h, Li is obtained after cooling1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder.Its average grain diameter is 6 μm.
3rd, 0.53gLiOH, 1.37g H are weighed3BO3、2.55g NH4H2PO4Deionization is scattered in 1.13g tetraethyl orthosilicates
The aqueous solution is formed in water, adds the Li of the above-mentioned preparations of 15g1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder, strong stirring is uniform, and
It is 10 with the pH value of 2mol/L ammoniacal liquor regulation systems, forms homogeneous gel and be coated on Li1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder
On body particle, the precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1100 DEG C are warming up to 2 DEG C/min programming rate and is incubated 20 hours, and required solid electrolyte sheet is just obtained after cooling
A5, obtained sheathing material are Li0.8B0.8Si0.2P0.8O4, solid electrolyte gross mass 10wt% is accounted for, the thickness of sheathing material is
25nm。
Embodiment 6
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, solid electrolyte sheet A6 is prepared using method and step same as Example 4.Different is to weigh
2.4gLi2CO3Powder, 1.7g Y2O3Powder, 6.8g TiO2Powder and 17.25g NH4H2PO4Li is made1.3Y0.3Ti1.7
(PO4)3Inner nuclear material powder, 400rpm ball millings 5h makes its average grain diameter be 8 μm in planetary ball mill.Added in the aqueous solution
The Li of the above-mentioned preparations of 20g1.3Y0.3Ti1.7(PO4)3Inner nuclear material powder, the thickness of the sheathing material of formation is 15nm.
Embodiment 7
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 2.5gLi is weighed respectively2CO3Powder, 0.80g Al2O3Powder, 7.08g TiO2Powder and 18g NH4H2PO4,
Ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 850 DEG C of preliminary calcinings
12h, Li is obtained after cooling1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder.Its average grain diameter is 10 μm.
3rd, 0.15gLiOH, 0.37g H are weighed3BO3、0.68g NH4H2PO4Deionization is scattered in 0.31g tetraethyl orthosilicates
In water, the Li of the above-mentioned preparations of 20g is added1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder, strong stirring is uniform, and with 2mol/L ammonia
The pH value of water regulation system is 11, forms homogeneous gel and is coated on Li1.3Al0.3Ti1.7(PO4)3On inner nuclear material powder granule, warp
The precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1100 DEG C are warming up to 2 DEG C/min programming rate and is incubated 20 hours, and required solid electrolyte sheet is just obtained after cooling
A7, obtained sheathing material are Li0.65B0.8Si0.05P0.95O4, solid electrolyte gross mass 5wt% is accounted for, the thickness of sheathing material is
12nm。
Embodiment 8
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 6.25gLi is weighed respectively2CO3Powder, 2g Al2O3Powder, 17.7g TiO2Powder and 45g NH4H2PO4, ball
Mill is well mixed.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then is placed in Muffle furnace and calcines 10h at 950 DEG C,
Li is obtained after cooling1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder；Its average grain diameter is 0.5 μm.
3rd, 0.044gLiOH, 0.11g H are weighed3BO3、0.21g NH4H2PO4With 0.09g tetraethyl orthosilicates be scattered in from
In sub- water, the Li of the above-mentioned preparations of 50g is added1.3Al0.3Ti1.7(PO4)3Inner nuclear material powder, strong stirring is uniform, and uses 2mol/L
The pH value of ammoniacal liquor regulation system is 8, forms homogeneous gel and is coated on Li1.3Al0.3Ti1.7(PO4)3On inner nuclear material powder granule,
The precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1050 DEG C are warming up to 2 DEG C/min programming rate and is incubated 12 hours, and required solid electrolyte sheet is just obtained after cooling
A8, obtained sheathing material are Li0.7B0.8Si0.1P0.9O4, solid electrolyte gross mass 0.5wt% is accounted for, the thickness of sheathing material is
20nm。
Embodiment 9
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 1.35gLi is weighed respectively2CO3Powder, 0.53g Al2O3Powder, 3.32g TiO2Powder and 8.97g
NH4H2PO4, ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 900 DEG C of preliminary calcinings
8h, Li is obtained after cooling1.4Al0.4Ti1.6(PO4)3Inner nuclear material powder；Its average grain diameter is 0.8 μm.
3rd, 0.16gLiOH, 0.36g H are weighed3BO3、0.59g NH4H2PO4Deionization is scattered in 0.46g tetraethyl orthosilicates
In water, the Li of the above-mentioned preparations of 10g is added1.4Al0.4Ti1.6(PO4)3Inner nuclear material powder, strong stirring is uniform, and with 2mol/L ammonia
The pH value of water regulation system is 9, forms homogeneous gel and is coated on Li1.4Al0.4Ti1.6(PO4)3On inner nuclear material powder granule, warp
The precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1150 DEG C are warming up to 2 DEG C/min programming rate and is incubated 8 hours, and required solid electrolyte sheet is just obtained after cooling
A9, obtained sheathing material are Li0.9B0.8Si0.3P0.7O4, solid electrolyte gross mass 8wt% is accounted for, the thickness of sheathing material is
23nm。
Embodiment 10
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 1.59gLi is weighed respectively2CO3Powder, 0.33g La2O3Powder, 6.23g TiO2Powder and 13.8g
NH4H2PO4, ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then is placed in Muffle furnace and calcines 16h at 750 DEG C,
Li is obtained after cooling1.05La0.05Ti1.95(PO4)3Inner nuclear material powder；Its average grain diameter is 1 μm.
3rd, 0.13gLiOH, 0.36g H are weighed3BO3、0.67g NH4H2PO4Deionization is scattered in 0.29g tetraethyl orthosilicates
In water, the Li of the above-mentioned preparations of 12g is added1.05La0.05Ti1.95(PO4)3Inner nuclear material powder, strong stirring is uniform, and uses 2mol/L
The pH value of ammoniacal liquor regulation system is 10, forms homogeneous gel and is coated on Li1.05La0.05Ti1.95(PO4)3Inner nuclear material powder granule
On, the precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1200 DEG C are warming up to 2 DEG C/min programming rate and is incubated 8 hours, and required solid electrolyte sheet is just obtained after cooling
A10, obtained sheathing material are LiB0.8Si0.4P0.6O4, solid electrolyte gross mass 5wt% is accounted for, the thickness of sheathing material is
30nm。
Embodiment 11
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 2.63gLi is weighed respectively2CO3Powder, 0.49g Cr2O3Powder, 9.83g TiO2Powder and 22.33g
NH4H2PO4, ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 950 DEG C of preliminary calcinings
4h, Li is obtained after cooling1.1Cr0.1Ti1.9(PO4)3Powder.Its average grain diameter is 1.5 μm.
3rd, 0.36gLiOH, 0.68g H are weighed3BO3、0.79g NH4H2PO4Deionization is scattered in 1.43g tetraethyl orthosilicates
In water, the Li of the above-mentioned preparations of 25g is added1.1Cr0.1Ti1.9(PO4)3Inner nuclear material powder, strong stirring is uniform, and with 2mol/L ammonia
The pH value of water regulation system is 11, forms homogeneous gel and is coated on Li1.1Cr0.1Ti1.9(PO4)3On inner nuclear material powder granule, warp
The precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
900 DEG C are warming up to 2 DEG C/min programming rate and is incubated 24 hours, and required solid electrolyte sheet is just obtained after cooling
A11, obtained sheathing material are Li1.1B0.8Si0.5P0. 5O4, solid electrolyte gross mass 6wt% is accounted for, the thickness of sheathing material is
20nm。
Embodiment 12
The present embodiment is used to illustrate solid electrolyte disclosed by the invention and preparation method thereof.
1st, 3.08gLi is weighed respectively2CO3Powder, 1.06gIn2O3Powder, 11.5g TiO2Powder and 26.22g
NH4H2PO4, ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 900 DEG C of preliminary calcinings
8h, Li is obtained after cooling1.1In0.1Ti1.9(PO4)3Inner nuclear material powder.Its average grain diameter is 3 μm.
3rd, 0.56gLiOH, 1.28g H are weighed3BO3、2.08g NH4H2PO4Deionization is scattered in 1.61g tetraethyl orthosilicates
In water, the Li of the above-mentioned preparations of 30g is added1.1In0.1Ti1.9(PO4)3Inner nuclear material powder, strong stirring is uniform, and with 2mol/L ammonia
The pH value of water regulation system is 8, forms homogeneous gel and is coated on Li1.1In0.1Ti1.9(PO4)3On inner nuclear material powder granule, warp
The precursor material with core shell structure is obtained after drying.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1150 DEG C are warming up to 2 DEG C/min programming rate and is incubated 8 hours, and required solid electrolyte sheet is just obtained after cooling
A12, obtained sheathing material are Li0.9B0.8Si0.3P0.7O4, solid electrolyte gross mass 8wt% is accounted for, the thickness of sheathing material is
25nm。
Comparative example 1
Li is prepared using method and step same as Example 41.3Al0.3Ti1.7(PO4)3Powder, by Li1.3Al0.3Ti1.7(PO4)3
Powder compression molding, is fitted into alumina crucible, then is placed in Muffle furnace and is warming up to 1100 DEG C with 2 DEG C/min programming rate
And 20 hours are incubated, Li is just obtained after cooling1.3Al0.3Ti1.7(PO4)3Electrolyte sheet DA1.
Comparative example 2
Li is prepared according to the method in CN101894972A embodiments 13.76Al0.36Zn0.07Ti1.32Si0.25P2.39O11.3S0.7
Electrolyte sheet CA2.
Comparative example 3
1st, 1.73gLi is weighed respectively2CO3Powder, 0.22g Al2O3Powder, 10g ZrO2Powder and 14.73g NH4H2PO4, ball
Mill is well mixed.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 800 DEG C of preliminary calcinings
6h, it is Li that chemical formula is obtained after cooling1.1Al0.1Zr1.9(PO4)3Inner nuclear material powder.Its average grain diameter is 5 μm.
3rd, 0.53gLiOH, 0.18g H are weighed3BO3With 0.13g NH4H2PO4It is scattered in deionized water and forms the aqueous solution,
Add the Li of the above-mentioned preparations of 20g1.1Al0.1Zr1.9(PO4)3Inner nuclear material powder, strong stirring is uniform, and is adjusted with 2 mol/L ammoniacal liquor
The pH value of section system is 11, forms homogeneous gel and is coated on Li1.1Al0.1Zr1.9(PO4)3On inner nuclear material powder granule, through drying
The precursor material with core shell structure is obtained afterwards.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1000 DEG C are warming up to 2 DEG C/min programming rate and is incubated 24 hours, and required solid electrolyte sheet is just obtained after cooling
CA3, obtained sheathing material are Li0.6B0.8PO4, solid electrolyte gross mass 2wt% is accounted for, the thickness of sheathing material is 30nm.
Comparative example 4
1st, 2.1gLi is weighed respectively2CO3Powder, 0.26g Al2O3Powder, 7.86g TiO2Powder and 17.86g NH4H2PO4,
Ball milling mixing is uniform.
2nd, the powder that step 1 is well mixed is fitted into alumina crucible, then be placed in Muffle furnace in 800 DEG C of preliminary calcinings
6h, it is Li that chemical formula is obtained after cooling1.1Al0.1Ti1.9(PO4)3Inner nuclear material powder.Its average grain diameter is 5 μm.
3rd, 0.53gLiOH, 0.18g H are weighed3BO3With 0.13g NH4H2PO4It is scattered in deionized water and forms the aqueous solution,
Add the Li of the above-mentioned preparations of 20g1.1Al0.1Ti1.9(PO4)3Inner nuclear material powder, strong stirring is uniform, and is adjusted with 2mol/L ammoniacal liquor
The pH value of section system is 11, forms homogeneous gel and is coated on Li1.1Al0.1Ti1.9(PO4)3On inner nuclear material powder granule, through drying
The precursor material with core shell structure is obtained afterwards.
4th, by the precursor material compression molding of the core shell structure of gained, it is fitted into alumina crucible, then be placed in Muffle furnace
1000 DEG C are warming up to 2 DEG C/min programming rate and is incubated 24 hours, and required solid electrolyte sheet is just obtained after cooling
CA4, obtained sheathing material are Li0.6B0.8PO4, solid electrolyte gross mass 2wt% is accounted for, the thickness of sheathing material is 30nm.
Lithium ion battery：
The solid electrolyte A1-A12 and CA1-CA4 being prepared respectively using embodiment 1-12 and comparative example 1-4 as electrolyte, with
Lithium metal is negative pole, with LiNi0.5Mn1.5O4All-solid lithium battery S1-S12 and DS1-DS4 is made for positive pole, preparing for battery is equal
Implement under the protection of argon gas atmosphere.Specific preparation process is as follows：First, A1-A12 and CA1-CA4 polishes on 800# sand paper
It is extremely smooth, it is ultrasonically treated 10 minutes in ethanol, and dried at 70 DEG C, obtain the solid electrolyte sheet of clean surface.By 1000
Gram positive electrode active materials LiNi0.5Mn1.5O4, 50 grams of bonding agent SBR, 30 grams of acetylene blacks, 10 grams of conductive agent HV be added to 1500 grams
In the anhydrous heptane of solvent, then stirred in de-airing mixer, form the anode sizing agent of stable uniform.Anode sizing agent is coated to
On the surface of solid electrolyte, and metal lithium sheet is attached to another surface of solid electrolyte.Finally, respectively in side of the positive electrode and negative
Pole side is plus aluminium foil and copper foil as collector.Said structure is encapsulated in stainless steel casing, completes all-solid lithium-ion battery
Making.
Performance test
1st, ionic conductivity
Solid electrolyte A1-A12 and CA1-CA4 that embodiment 1-12 and comparative example 1-4 are prepared two sides are sputtered respectively
Last layer golden film is as conductive electrode（Blocking electrode）, then on electrochemical workstation determination sample room temperature AC impedance,
The test of AC impedance is from high frequency 105Hz to low frequency 1Hz, then draw total total resistance R of electrolyte（Including body electricity
Resistance and grain boundary resistance）, in spectrogram on the right of circular arc corresponding to real part（X axles）Value be the electrolyte total resistance.According to solid
The calculation formula of state electrolyte ion electrical conductivity：σ=L/A·R（Wherein L is the thickness of solid electrolyte sheet, and A is the face of golden film
Product, R is solid electrolyte total resistance value, and L value is 0.2cm, and A value is 1.76cm2.）,
Corresponding ionic conductivity is calculated.It the results are shown in Table 1.
2nd, electrochemical window
The solid electrolyte A1-A12 and CA1-CA4 two sides that embodiment 1-12 and comparative example 1-4 are prepared is suppressed respectively
Lithium piece and platinized platinum, the cyclic voltammetry curve of the half-cell is determined on electrochemical workstation, so as to determine the electricity of prepared sample
Chemical window, the results are shown in Table 1.
3rd, battery performance
Discharge capacity first：By all-solid lithium battery S1-S12 and DS1-DS4, blue strange BK-6016 battery performance test instrument is used
（Guangzhou Lanqi Electronic Industrial Co., Ltd.）Tested, test result is shown in Table 2.
Method of testing is as follows：At 25 ± 1 DEG C, by battery with 0.1C electric currents constant-current charge to 4.7V, then turn constant voltage
Charging, cut-off current 0.05C；Then, then by battery with 0.1C electric currents constant-current discharge to 3.0V, obtain battery normal temperature 0.1C electricity
Stream is discharged to 3.0V capacity, using the ratio of the discharge capacity and the quality of positive active material as first discharge specific capacity.
Table 1
Table 2
From table 1 it follows that the Li that comparative example 1 is prepared1.3Al0.3Ti1.7(PO4)3The total ion-conductance of room temperature of electrolyte
Conductance is σ=1.43 × 10-4S·cm-1, electrochemical window 2.5V, match negative pole such as lithium of the current potential less than 2.5V and make negative pole
Short circuit phenomenon occurs；And the core shell structure Li that corresponding embodiment 4 is prepared1.3Al0.3Ti1.7(PO4)3（Shell is 5wt%
Li0.8B0.8Si0.2P0.8O4）The total ionic conductivity of room temperature of electrolyte is σ=3.02 × 10-4S·cm-1, electrochemical window ＞
5V；The core shell structure Li that embodiment 5 is prepared1.3Al0.3Ti1.7(PO4)3（Shell is 10wt% Li0.8B0.8Si0.2P0.8O4）
The total ionic conductivity of room temperature of electrolyte is σ=2.16 × 10-4S·cm-1, electrochemical window ＞ 5V, it is seen then that in Li1+ x M x Ti2-x (PO4)3Surface sets one layer of Li0.6+yB0.8SiyP1-yO4Electronic shield layer, can make external electrical masked by shell and
Do not enter kernel, effectively avoid the generation of inner nuclear material redox reaction, improve the electrochemical window of material.
Li simultaneously0.6+yB0.8SiyP1-yO4Also there is high ionic conductivity, do not interfere with conduction of the lithium ion in shell.Therefore it is described
Lithium ion solid electrolyte there is wide electrochemical window（Electrochemical window ＞ 5V）Higher ionic conductivity, have very
It is widely applied.
It can be seen from the results above that the present invention uses Li0.6+yB0.8SiyP1-yO4Coat Li1+xMxTi2-x(PO4)3Shell
Material can sufficiently the face of progress contacts with inner nuclear material, complete fine and close electronic shield layer is formed on inner nuclear material surface, very
Good solves Ti4+It is reduced to Ti3+The problem of.Obtained solid electrolyte has wide electrochemical window（Electrochemical window
＞ 5V）, higher ionic conductivity and low electronic conductivity, discharge capacity is high first for the battery of preparation.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (17)
1. a kind of lithium ion battery solid electrolyte, it is characterised in that including inner nuclear material and be coated on outside the inner nuclear material
The sheathing material on surface；The inner nuclear material includes Li1+xMxTi2-x(PO4)3, wherein, M is in Al, La, Cr, Ga, Y or In
At least one, 0.05 ￡ x£0.4；, the sheathing material includes Li0.6+yB0.8SiyP1-yO4, wherein, 0.01 ￡ y£0.5。
2. solid electrolyte according to claim 1, it is characterised in that the ionic conductivity of the sheathing material is 10- 6More than S/cm, electronic conductivity are less than 10-10S/cm。
3. solid electrolyte according to claim 2, it is characterised in that the ionic conductivity of the sheathing material is 10-6~
10-5S/cm。
4. solid electrolyte according to claim 1, it is characterised in that the sheathing material is selected from
Li0.65B0.8Si0.05P0.95O4、Li0.7B0.8Si0.1P0.9O4、Li0.8B0.8Si0.2P0.8O4、Li0.9B0.8Si0.3P0.7O4、
LiB0.8Si0.4P0.6O4Or Li1.1B0.8Si0.5P0.5O4At least one of.
5. according to the solid electrolyte described in any one in claim 1-4, it is characterised in that the thickness of the sheathing material
For 10 ~ 30nm.
6. according to the solid electrolyte described in any one in claim 1-4, it is characterised in that with the solid electrolyte
On the basis of gross weight, the content of the sheathing material is 0.5 ~ 10wt%.
7. solid electrolyte according to claim 1, it is characterised in that the inner nuclear material is selected from Li1.1Y0.1Ti1.9
(PO4)3、Li1.3Y0.3Ti1.7(PO4)3、Li1.4Y0.4Ti1.6(PO4)3、Li1.1Al0.1Ti1.9(PO4)3、Li1.3Al0.3Ti1.7
(PO4)3、Li1.05La0.05Ti1.95(PO4)3、Li1.1Cr0.1Ti1.9(PO4)3、Li1.1Ga0.1Ti1.9(PO4)3Or Li1.1In0.1Ti1.9
(PO4)3At least one of.
8. according to the solid electrolyte described in any one in claim 1-4,7, it is characterised in that the inner nuclear material is put down
Equal particle diameter is 0.5 ~ 10 μm.
9. the preparation method of the solid electrolyte as described in any one in claim 1-8, it is characterised in that step includes：
S1, inner nuclear material is obtained, the inner nuclear material includes Li1+xMxTi2-x(PO4)3, wherein, M be selected from Al, La, Cr, Ga, Y or
At least one of In, 0.05 ￡ x£0.4；
S2, the inner nuclear material mixed with the solution containing shell lithium source, shell phosphate, silicon source and boron source, adjust pH value
For 8 ~ 11, dry precursor material；
S3, the precursor material calcined, the solid electrolyte is obtained after cooling.
10. the preparation method of solid electrolyte according to claim 9, it is characterised in that the temperature of the calcining is 900
~ 1200 DEG C, the time is 8 ~ 24h.
11. the preparation method of solid electrolyte according to claim 9, it is characterised in that the inner nuclear material is selected from
Li1.1Y0.1Ti1.9(PO4)3、Li1.3Y0.3Ti1.7(PO4)3、Li1.4Y0.4Ti1.6(PO4)3、Li1.1Al0.1Ti1.9(PO4)3、
Li1.3Al0.3Ti1.7(PO4)3、Li1.05La0.05Ti1.95(PO4)3、Li1.1Cr0.1Ti1.9(PO4)3、Li1.1Ga0.1Ti1.9(PO4)3Or
Li1.1In0.1Ti1.9(PO4)3At least one of；The average grain diameter of the inner nuclear material is 0.5 ~ 10 μm.
12. the preparation method of solid electrolyte according to claim 9, it is characterised in that in being obtained in the step S1
The method of nuclear material includes, and titanium source, metal M sources, kernel lithium source, kernel phosphate are mixed and tentatively calcined, obtains institute
State inner nuclear material；
By element Li, metal M, Ti, P molar content in terms of, the kernel lithium source, metal M sources, titanium source, kernel is phosphatic contains
Amount the ratio between be（1+x）~1.2（1+x）：x：（2-x）：3.
13. the preparation method of solid electrolyte according to claim 12, it is characterised in that the precalcined temperature
For 750 ~ 950 DEG C, the time is 4 ~ 16h.
14. the preparation method of solid electrolyte according to claim 12, it is characterised in that the titanium source is selected from TiO2；
The metal M sources are selected from Al2O3、Y2O3、Ga2O3、La2O3、Cr2O3、In2O3In one or more；
The one kind or more of the kernel lithium source in lithium carbonate, lithium hydroxide, a hydronium(ion) lithia, lithium nitrate, lithium acetate
Kind；
The kernel phosphate is selected from NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、H3PO4In one or more.
15. the preparation method of solid electrolyte according to claim 9, it is characterised in that in the step S2, with element
Molar content meter, element Li in the solution containing shell lithium source, shell phosphate, silicon source and boron source：B : Si：P be 0.65 ~
1.1：0.8：（y）：（1-y）, wherein, 0.01 ￡ y£0.5。
16. the preparation method of solid electrolyte according to claim 9, it is characterised in that the boron source is selected from H3BO3、
B2O3、LiBO2, one or more in triethyl borate；
The one kind or more of the shell lithium source in lithium carbonate, lithium hydroxide, a hydronium(ion) lithia, lithium nitrate, lithium acetate
Kind；
The shell phosphate is selected from NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、H3PO4In one or more；
The silicon source is tetraethyl orthosilicate.
17. a kind of lithium ion battery, it is characterised in that including positive pole, negative pole and be arranged at consolidating between the positive pole and negative pole
State electrolyte；
The solid electrolyte is the lithium ion battery solid electrolyte described in any one in claim 1-8.
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