CN104659412B - Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery - Google Patents
Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery Download PDFInfo
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- CN104659412B CN104659412B CN201510048102.5A CN201510048102A CN104659412B CN 104659412 B CN104659412 B CN 104659412B CN 201510048102 A CN201510048102 A CN 201510048102A CN 104659412 B CN104659412 B CN 104659412B
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Abstract
The invention discloses a lithium-carbon-boron oxide solid electrolyte material containing a plane triangle group and a battery. A chemical general formula of the material is Li＜2+x＞CzBbMmO＜3-n＞Yn, wherein each C or B or M and adjacent three Os form a plane triangle structure; or each C or B or M and the adjacent three Ys form the plane triangle structure; M is an element for doping and substituting Li or C or B; Y is an element for doping and substituting O; M specifically is one or more of Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge and Zr; the Y specifically is one or more of S, N and F; x, z, b, m and n are respectively the molar percents accounted by the corresponding elements; x is smaller than or equal to 1 and greater than or equal to 0; z is smaller than or equal to 1 and greater than or equal to 0.3; b is smaller than or equal to 1 and greater than or equal to 0; m is smaller than or equal to 0.2 and greater than or equal to 0; and n is smaller than or equal to 0.5 and greater than or equal to 0.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of lithium carbon boron oxide compound solid-state containing plane triangle group
Electrolyte and battery.
Background technology
Development and electrical network energy storage, the development of small-sized energy storage demand recently as electric automobile, exploitation can be in width
Temperature range use, the battery with higher-security, high-energy-density and power density is very necessary.
Lithium ion battery be applied as chemical energy storage mode and develop it is relatively later, but because its is lightweight, specific energy
The features such as high, specific power height, life-span length, is considered one of most competitive electrochemical energy storage technology.Existing commercial lithium from
Sub- battery mainly includes two types：A kind of is that one kind is to adopt gel electrolyte using the lithium ion battery of liquid electrolyte
Lithium ion battery.Liquid electrolyte possesses higher conductivity at room temperature with gel electrolyte, and electrolyte can be effective
Infiltration electrode particle, and stable solid electrolyte film (SEI) can be formed in both positive and negative polarity electrode surface.Therefore existing commercial lithium
Ion battery has the low internal resistance of cell and cyclical stability near room temperature.But liquid organic electrolyte low-temperature conductivity can show
Write and decline, therefore when the temperature decreases the internal resistance of cell can be significantly increased, it is impossible to meet the application requirement under cryogenic conditions.Work as battery
When external temperature rising, high current charge-discharge or short circuit cause internal temperature of battery to raise, the change between electrolyte and electrode
Reaction speed aggravation is learned, heat is further produced, causes thermal runaway.This process can also produce gas, ultimately result in battery close
Envelope failure, flammable gas and organic solvent runs at high temperature oxygen and also on fire can explode.It is electrolysed in the electrolyte of gel-type
The content of liquid is relatively fewer, and security performance increases, but cannot fundamentally solve safety issue.Liquid electrolyte is low
Current potential can be reduced and form solid electrolyte film in negative terminal surface, cause battery charging and discharging coulombic efficiency relatively low.Additionally, due to mesh
LiPF is typically adopted in front commercial li-ion battery electrolyte system6As electrolytic salt, LiPF6Heat endurance is poor, and and water
Reaction can generate HF, cause degradation of cell performance.At present conventional organic electrolyte system electrochemical window is limited, limit lithium from
The further raising of the operating voltage of sub- battery.Therefore the energy density and power density of output are limited.
In recent years, jumbo lithium ion battery occurs in that serious safety in terms of electric automobile, aircraft auxiliary power
Accident, these are all relevant using flammable organic solvent with lithium ion battery.Although by addition fire retardant, adopting high temperature resistant
Ceramic diaphragm, positive and negative pole material surface modification and can carry to a certain extent in the coating measure such as fire proofing of battery core appearance
The security of high existing lithium ion battery, but cannot fundamentally ensure the security of lithium ion battery.
For the safety issue for overcoming existing commercial liquid lithium ion battery to face, many mechanisms are devoted to research
Solid lithium ion battery based on solid electrolyte material.Relative to liquid electrolyte, solid electrolyte is non-volatile, nonflammable,
Safety issue can fundamentally be solved using solid electrolyte.Solid electrolyte can keep good within the scope of wide temperature
Good stability, so solid state battery can work within the scope of wide temperature.And some solid electrolyte materials are to moisture
Oxygen is insensitive, and good chemical stability, therefore the mistake that solid state battery is prepared in production can be for a long time kept in atmosphere
Protective atmosphere can not be used in journey, production cost is reduced.And solid electrolyte has very wide electrochemical window, compares liquid
State electrolyte is more resistant to high voltage, therefore solid state battery can use high-tension positive electrode, so as to improve battery energy density.
The porous septum of gel electrolyte and immersion liquid electrolyte relative to porous, solid electrolyte is fine and close, and with very high
Intensity and hardness, can effectively prevent the puncture of Li dendrite, therefore improve the security of battery.To sum up, using solid electricity
The battery of solution matter, may have excellent security, good cycle characteristics and higher energy density.
Solid electrolyte includes copolymer solid electrolyte, inorganic solid electrolyte and composite solid electrolyte.Polymerization
Thing has good tensile property, using the solid state battery of solid polyelectrolyte can be prepared into the flexible of various shapes and
Can deformation battery.But because polymer dielectric just has higher ionic conductivity only more than glass transition temperature,
Therefore the operating temperature of polymer battery is limited, and in addition the polyethylene glycol oxide (PEO) stable with lithium metal conventional at present is polymerized
Thing electrolyte, electrochemical window is narrower, therefore the all-solid-state battery of PEO polymer can not adopt high-voltage electrode material, limit
The output voltage and energy density of battery.Inorganic solid electrolyte be a class have compared with macroion transmission characteristic it is inorganic fast from
Sub- conductor material, it has higher mechanical strength, and Li dendrite can be prevented to penetrate the internal short-circuit that electrolyte is caused.Inorganic solid-state
Electrolyte can be prepared into difference by methods such as ceramic post sintering, ald, magnetron sputtering, vapour deposition, flow casting moldings
Thickness dielectric substrate of different shapes or film.Relative to solid polyelectrolyte, inorganic solid electrolyte can be wider
Within the temperature range of keep chemical stability, therefore the battery based on inorganic solid electrolyte has with high security.And
The electrochemical window of inorganic solid electrolyte also compared with solid polyelectrolyte width, in going for high-tension battery.
In sum, had relative to the battery of liquid electrolyte using the solid state battery of inorganic solid electrolyte higher
Security.But the maximum shortcoming compared with liquid electrolyte of inorganic solid electrolyte is exactly that ionic conductivity is relatively low, so as to lead
The internal resistance of cause solid state battery is larger, and cycle performance is poor.At present, inorganic solid electrolyte ionic conductivity highest is Kamaya
The Li of report10GeP2S12(LAGP)(Kamaya,et al.,2011,Nature Material,A lithium superionic
conductor).But from from the perspective of practical application, sulfide easily has poison gas with the water generation that reacts in air
Body H2S.So, at present each research institution is just devoted to research while meeting high ionic conductivity, wide electrochemical window, high chemistry
The novel inorganic solid electrolyte and the solid state battery using inorganic solid electrolyte of the performances such as stability.
The content of the invention
Embodiments provide a kind of lithium carbon boron oxide compound solid electrolyte material with plane triangle group
And battery, with electrochemical stability, chemical stability, storage stability, high-temperature stability, relatively low electronic conductivity,
There is higher ionic conductivity under high temperature.Can be in wide temperature using the lithium ion battery of the solid electrolyte material of the present invention
Work under degree scope, particularly work at high temperature, can be used as one-shot battery, it is also possible to use as secondary cell.With this
Solid electrolyte material is the lithium ion battery of electrolyte, due to not containing organic electrolyte, and fundamentally solves current business
With the safety issue of lithium ion battery.
In a first aspect, embodiments providing a kind of lithium carbon boron oxide compound solid state electrolysis containing plane triangle group
Material, chemical general formula is：Li2+xCzBbMmO3-nYn；
Wherein, each C or B or M and adjacent three O constitutes a plane triangle structure, or each C or B or M with
Three adjacent Y constitute a plane triangle structure；M is to be doped substituted element to Li or C or B；Y is that O is carried out
The element of doped and substituted；The M is specially Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, one or more in Zr；The Y
Specially S, N, one or more in F；The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤
1,0.3≤z≤1,0≤b≤1,0≤m≤0.2,0≤n≤0.5；The proterties of the material is：It is powder body material, block materials, thin
Any one in membrane material or composite.
Preferably, in Raman spectrum, in 700cm-1Above 1200cm-1Region below has peak；In infrared spectrum,
750cm-1Above 1500cm-1Region below has peak.
In second aspect, a kind of group containing plane triangle as described in above-mentioned first aspect is embodiments provided
Lithium carbon boron oxide compound solid electrolyte material preparation method, the material is powder body material, and methods described includes：
By Li sources, C sources, B sources, M sources, Y sources according to Li2+xCzBbMmO3-nYnMolar ratio ingredient, forms presoma；The M tools
Body is Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, one or more in Zr；The Y is specially S, N, one kind in F or
It is various；The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤1,0.3≤z≤1,0≤b≤1,0
≤ m≤0.2,0≤n≤0.5；
Handle mill or planetary ball mill or high-energy ball milling is well mixed, obtain precursor powder；
The precursor powder is pre-processed 1～12 hour in 100 DEG C～500 DEG C air atmospheres；
Precursor powder after heat treatment is carried out again hand mill or planetary ball mill or high-energy ball milling；
Sinter 24～336 hours at 500 DEG C～650 DEG C, that is, obtain the powder body material.
In the third aspect, a kind of group containing plane triangle as described in above-mentioned first aspect is embodiments provided
Lithium carbon boron oxide compound solid electrolyte material preparation method, the material is powder body material, and methods described includes：
By Li sources, C sources, B sources, M sources, Y sources according to Li2+xCzBbMmO3-nYnMolar ratio ingredient, forms presoma；The M tools
Body is Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, one or more in Zr；The Y is specially S, N, one kind in F or
It is various；The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤1,0.3≤z≤1,0≤b≤1,0
≤ m≤0.2,0≤n≤0.5；
Handle mill or planetary ball mill or high-energy ball milling is well mixed, obtain precursor powder；
The precursor powder is pre-processed 1～12 hour in 100 DEG C～500 DEG C air atmospheres；
Precursor powder after heat treatment is carried out again hand mill or planetary ball mill or high-energy ball milling；
Sinter 1～24 hour at 500 DEG C～650 DEG C, then carry out hand mill or planetary ball mill or high-energy ball milling；
Sinter 1～24 hour at 500 DEG C～650 DEG C again, that is, obtain the powder body material.
In fourth aspect, a kind of group containing plane triangle as described in above-mentioned first aspect is embodiments provided
Lithium carbon boron oxide compound solid electrolyte material preparation method, the material is block materials, and methods described includes：
After the powder body material mechanical compression molding that above-mentioned second aspect or third aspect methods described are prepared,
500 DEG C～650 DEG C re-sinter 6～12 hours, obtain the block materials.
5th aspect, embodiments provide it is a kind of as described in above-mentioned first aspect containing plane triangle group
The preparation method of lithium carbon boron oxide compound solid electrolyte material, the material is block materials, and methods described includes：
The powder body material that above-mentioned second aspect or third aspect methods described are prepared is put into into compression mold, using etc.
The method of warm static pressure, at 500 DEG C～650 DEG C, suppresses 2～6 hours under 1MPa～6MPa, obtains the block materials.
6th aspect, embodiments provide it is a kind of as described in above-mentioned first aspect containing plane triangle group
The preparation method of lithium carbon boron oxide compound solid electrolyte material, the material is block materials, and methods described includes：
After the powder body material melting that above-mentioned second aspect or third aspect methods described are prepared, in pouring mould into,
Cooling, obtains the block materials.
7th aspect, embodiments provide it is a kind of as described in above-mentioned first aspect containing plane triangle group
The preparation method of lithium carbon boron oxide compound solid electrolyte material, the material is thin-film material, and methods described includes：
The powder body material that above-mentioned second aspect or third aspect methods described are prepared 3MPa～500MPa, 500
DEG C～650 DEG C under conditions of be pressed into dense target material, by magnetron sputtering, pulsed laser deposition, thermal evaporation or electron beam evaporation
Any one of prepare the thin-film material.
Eighth aspect, embodiments provide it is a kind of as described in above-mentioned first aspect containing plane triangle group
The preparation method of lithium carbon boron oxide compound solid electrolyte material, the material is composite, and methods described includes：
The powder body material that the claims 3 or 4 are prepared is combined with inorganic material, or powder body material, nothing
Machine material and organic material are combined, and obtain the composite；
Wherein, the inorganic material includes SiO2、Al2O3Or compound containing Li；The organic material includes polyethylene glycol oxide
One or more mixing in PEO, Kynoar PVDF, polyacrylonitrile (PAN), polymethyl methacrylate MMA.
9th aspect, embodiments provides a kind of lithium ion battery, including described in above-mentioned first aspect containing flat
The lithium carbon boron oxide compound solid electrolyte material of face triangle group.
Lithium carbon boron oxide compound solid electrolyte material with plane triangle group provided in an embodiment of the present invention, has
Electrochemical stability, chemical stability, storage stability, high-temperature stability, relatively low electronic conductivity, at high temperature with compared with
High ionic conductivity.Being capable of work over a wide range of temperatures using the lithium ion battery of the solid electrolyte material of the present invention
Make, particularly work at high temperature, can be used as one-shot battery, it is also possible to use as secondary cell.With the solid electrolyte
Material is the lithium ion battery of electrolyte, due to not containing organic electrolyte, and fundamentally solves current commercial li-ion electricity
The safety issue in pond.
Description of the drawings
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
Fig. 1 is Li provided in an embodiment of the present invention2.58C0.42B0.58O3Dusty material (on) and single crystal diffraction fitting (under)
XRD spectrum；
Fig. 2 is Li provided in an embodiment of the present invention2.58C0.42B0.58O3Atomic structure schematic diagram.
Fig. 3 is Li provided in an embodiment of the present invention2.58C0.42B0.58O3Thermogravimetric differential thermal curve；
Fig. 4 is Li provided in an embodiment of the present invention2.58C0.42B0.58O3The curve that varies with temperature of electrical conductivity；
Fig. 5 is Li provided in an embodiment of the present invention2.58C0.42B0.58O3Cyclic voltammetry curve；
Fig. 6 is a kind of lithium carbon boron oxide compound solid electrolyte containing plane triangle group that the embodiment of the present invention 2 is provided
The preparation method of material；
Fig. 7 is lithium carbon boron oxide compound solid state electrolysis of the another kind containing plane triangle group that the embodiment of the present invention 3 is provided
The preparation method of material.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but is not intended to limit the guarantor of the present invention
Shield scope.It should be noted that the lithium ion battery described in various embodiments of the present invention, including negative pole is using the lithium electricity of lithium metal
Pond, and negative pole is using the lithium ion battery of the nonmetallic lithiums such as graphite, silicon.
Embodiment 1
The embodiment of the present invention 1 provides a kind of lithium carbon boron oxide compound solid electrolyte material containing plane triangle group,
Its chemical general formula is：Li2+xCzBbMmO3-nYn；
Wherein, C refers to carbon, and B refers to boron element, and O refers to oxygen element；Each C or B or M constitutes one and puts down with three adjacent O
Face triangular structure, or each C or B or M and adjacent three Y, one plane triangle structure of composition；M is to Li or C or B
It is doped substituted element；Y is that substituted element is doped to O；The M is specially Na, K, Mg, Ca, Al, Ga, La, Y,
Si, Ge, one or more in Zr；The Y is specially S, N, one or more in F；The x, z, b, m, n are respectively right
Answer the molar percentage shared by element；0≤x≤1,0.3≤z≤1,0≤b≤1,0≤m≤0.2,0≤n≤0.5；
Lithium carbon boron oxide compound solid electrolyte material containing plane triangle group provided in an embodiment of the present invention can have
Body is：Powder body material, block materials, thin-film material or composite.
In Raman spectrum, in 700cm-1Above 1200cm-1Region below has peak；In infrared spectrum, in 750cm-1With
Upper 1500cm-1Region below has peak.
It has been presented in Fig. 1 the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
Li2.58C0.42B0.58O3X-ray diffraction (X-ray diffraction, XRD) collection of illustrative plates, wherein curve above is to powder material
The X ray diffracting spectrum that material is carried out, curve below is that the collection of illustrative plates that X-ray diffraction is fitted is carried out to its monocrystalline, can be seen
Fit like a glove to the collection of illustrative plates that X-ray diffraction obtains is carried out to dusty material obtaining collection of illustrative plates with single crystal diffraction fitting.
Fig. 2 is Li2.58C0.42B0.58O3Atomic structure schematic diagram.
The Li that the present invention is provided2.58C0.42B0.58O3Material carries out thermogravimetric differential thermal test, thermogravimetric differential thermal curve such as Fig. 3 institutes
Show, it is found that material is substantially heat-staple below 700 DEG C.
(Fig. 4 is Li to carry out the test of ionic conductivity to the material that the present invention is provided2.58C0.42B0.58O3Electrical conductivity with
The curve of temperature change), and and Li2CO3Ionic conductivity carry out contrast discovery, the material electric conductivity ratio that the present invention is provided
Li2CO33 orders of magnitude are at least improve, and activation energy also has substantially reduction.
Cyclic voltammetry is carried out to the material that the present invention is provided, cyclic voltammetry curve is as shown in figure 5, find this material
Electrochemical window is very wide, in 0-5V vs.Li/Li+It is electrochemically stable.
Lithium carbon boron oxide compound solid electrolyte material with plane triangle group provided in an embodiment of the present invention, has
Electrochemical stability, chemical stability, storage stability, high-temperature stability, relatively low electronic conductivity, at high temperature with compared with
High ionic conductivity.Lithium ion battery with the solid electrolyte material as electrolyte, due to without organic electrolyte, and from
Fundamentally solve the safety issue of current commercial li-ion battery.
Embodiment 2
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
The preparation method of method, specially powder body material, as shown in fig. 6, including：
Step 201, by Li sources, C sources, B sources, M sources, Y sources according to Li2+xCzBbMmO3-nYnMolar ratio ingredient, forms presoma；
Specifically, the M can be Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, one or more in Zr；The Y
Can be S, N, one or more in F；The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤
1,0.3≤z≤1,0≤b≤1,0≤m≤0.2,0≤n≤0.5.
Step 202, handles mill or planetary ball mill or high-energy ball milling is well mixed, and obtains precursor powder；
Step 203, the precursor powder is pre-processed 1～12 hour in 100 DEG C～500 DEG C air atmospheres；
Step 204, the precursor powder after heat treatment is carried out again hand mill or planetary ball mill or high-energy ball milling；
Step 205, sinters 24～336 hours at 500 DEG C～650 DEG C, that is, obtain the powder body material.
The preparation method that the present embodiment is provided, can be used in preparing the base containing plane triangle described in above-described embodiment 1
The powder body material of the lithium carbon boron oxide compound solid electrolyte material of group.The particle size of the powder body material for preparing 10nm～
In the range of 500nm.The present embodiment provide method is simple, with low cost, application suitable for manufacturing on a large scale.
Embodiment 3
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
Another kind of preparation method of method, specially powder body material, as shown in fig. 7, comprises：
Step 301, by Li sources, C sources, B sources, M sources, Y sources according to Li2+xCzBbMmO3-nYnMolar ratio ingredient, forms presoma；
Specifically, the M can be Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, one or more in Zr；The Y
Can be S, N, one or more in F；The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤
1,0.3≤z≤1,0≤b≤1,0≤m≤0.2,0≤n≤0.5.
Step 302, handles mill or planetary ball mill or high-energy ball milling is well mixed, and obtains precursor powder；
Step 303, the precursor powder is pre-processed 1～12 hour in 100 DEG C～500 DEG C air atmospheres；
Step 304, the precursor powder after heat treatment is carried out again hand mill or planetary ball mill or high-energy ball milling；
Step 305, sinters 1～24 hour at 500 DEG C～650 DEG C, then carries out hand mill or planetary ball mill or high-energy ball milling；
Step 306, then sinter 1～24 hour at 500 DEG C～650 DEG C, obtain the powder body material.
The preparation method that the present embodiment is provided, can be used in preparing the base containing plane triangle described in above-described embodiment 1
The powder body material of the lithium carbon boron oxide compound solid electrolyte material of group.The particle size of the powder body material for preparing 10nm～
In the range of 500nm.The present embodiment provide method is simple, with low cost, application suitable for manufacturing on a large scale.
Embodiment 4
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
A kind of preparation method of method, specially block materials, including：
After the powder body material mechanical compression molding that above-described embodiment 2 or 3 is prepared, re-sinter at 500 DEG C～650 DEG C
6～12 hours, that is, obtain the block materials.
Specifically, the condition of mechanical compaction is：Pressure under room temperature using 2-50MPa is suppressed.
Embodiment 5
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
Another kind of preparation method of method, specially block materials, including：
The powder body material machinery that above-described embodiment 2 or 3 is prepared is put into compression mold, using the side of isothermal static pressure
Method, at 500 DEG C～650 DEG C, suppresses 2～6 hours under 1MPa～6MPa, that is, obtain the block materials.
Embodiment 6
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
Another preparation method of method, specially block materials, including：
After the powder body material high-temperature fusion that above-described embodiment 2 or 3 is prepared, in pouring mould into, cooling obtains described
Block materials.
Embodiment 7
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
The preparation method of method, specially thin-film material, including：
The powder body material that above-described embodiment 2 or 3 is prepared is under conditions of 3MPa～500MPa, 500 DEG C～650 DEG C
Be pressed into dense target material, by the methods such as magnetron sputtering, pulsed laser deposition (PLD), thermal evaporation or electron beam evaporation Si,
Pt、SiO2Deng preparing the thin-film material on substrate.
Embodiment 8
Present embodiments provide a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group
The preparation method of method, specially composite, including：
The powder body material that above-described embodiment 2 or 3 is prepared is combined with inorganic material, or powder body material, inorganic
Material and organic material are combined, and obtain the composite；
Wherein, include with the complex method of inorganic material：The above-mentioned lithium carbon boron oxide compound containing plane triangle group is consolidated
State electrolyte powder material, with inorganic material SiO2、Al2O3Or the material such as compound containing Li, handle mill or ball milling by a certain percentage
It is well mixed, obtains composite powder material.
Or, the preparation method with the above-mentioned lithium carbon boron oxide compound solid electrolyte film material containing plane triangle group
Similar, cosputtering obtains composite film material.
Include with the complex method of organic material：By the above-mentioned lithium carbon boron oxide compound solid state electrolysis containing plane triangle group
Matter powder body material and inorganic material SiO2、Al2O3Or compound containing Li etc., and organic material polyethylene glycol oxide (PEO), poly- inclined fluorine
Ethene (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) etc. are well mixed, in being dissolved in organic solvent, then will
Organic solvent is evaporated, and obtains compound electrolyte material.
The preparation method that the various embodiments described above are provided, can be used in preparing described in above-described embodiment 1 containing plane three
The composite of the lithium carbon boron oxide compound solid electrolyte material of angular group.Each method is simple, with low cost, applicable
In the application that can be manufactured on a large scale.
It is following to be prepared containing plane triangle group using method provided in an embodiment of the present invention with the explanation of multiple instantiations
The detailed process of lithium carbon boron oxide compound solid electrolyte material, and the method and battery behavior for being applied to lithium ion battery.
Embodiment 9
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte powder body material containing plane triangle group to illustrate
Detailed process.
Example 20 in molar ratio:9 weigh appropriate highly purified Li2CO3With H3BO3Powder, hand mill 1h is sufficiently mixed in mortar
After uniform, in being put into alumina crucible, crucible is put in Muffle furnace, is risen to 3 DEG C/min programming rates in air atmosphere
500 DEG C, room temperature is down to after insulation 12h, after hand mill is well mixed in mortar after taking-up, in being transferred to ball grinder, is added appropriate
Alcohol, ball milling 6h is dried at 50～70 DEG C, in being then placed in alumina crucible, crucible is put in Muffle furnace, in air gas
650 DEG C are risen to 3 DEG C/min programming rates in atmosphere, after insulation 336h room temperature is down to, obtain pure phase Li2.58C0.42B0.58O3。
Embodiment 10
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte powder body material containing plane triangle group to illustrate
Detailed process.
Example 20 in molar ratio:9 weigh appropriate highly purified Li2CO3With H3BO3Powder, hand mill 1h is sufficiently mixed in mortar
After uniform, in being put into alumina crucible, crucible is put in Muffle furnace, is risen to 3 DEG C/min programming rates in air atmosphere
500 DEG C, room temperature is down to after insulation 12h, after hand mill is well mixed in mortar after taking-up, in being transferred to ball grinder, is added appropriate
Alcohol, ball milling 6h is dried at 50～70 DEG C, in being then placed in alumina crucible, crucible is put in Muffle furnace, in air gas
650 DEG C are risen to 3 DEG C/min programming rates in atmosphere, after insulation 24h room temperature is down to, in mortar after hand mill 1h, place into oxidation
In aluminium crucible, crucible is put in Muffle furnace, 650 DEG C, after insulation 24h are risen to 3 DEG C/min programming rates in air atmosphere
Room temperature is down to, above step is repeated several times until obtaining pure phase Li2.58C0.42B0.58O3。
Embodiment 11
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte block materials containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3Powder body material Jing planetary ball mill 900r/min ball milling 3h, by the powder for obtaining the stainless of diameter 13mm is put into
In steel mold, 5min is suppressed with the pressure of 6Mpa using tablet press machine, the disk for obtaining is put in Muffle furnace, in air atmosphere
650 DEG C are risen to 3 DEG C/min programming rates, 6h is incubated, diameter 13mm, the block materials of thickness 0.5mm are obtained.
Embodiment 12
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte block materials containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3Powder body material Jing planetary ball mill 900r/min ball milling 3h, by the powder for obtaining the graphite of diameter 20mm is put into
In mould, 600 DEG C are risen to the speed of 5 DEG C/min in vacuum atmosphere with the pressure of 5MPa using isothermal static pressure machine, at 600 DEG C
Lower compacting 4h, obtains diameter 20mm, the block materials of thickness 1mm.
Embodiment 13
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte film material containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3Powder body material Jing planetary ball mill 900r/min ball milling 3h, by the powder for obtaining the graphite of diameter 50mm is put into
In mould, 600 DEG C are risen to the speed of 5 DEG C/min in vacuum atmosphere with the pressure of 5MPa using isothermal static pressure machine, at 600 DEG C
Lower compacting 4h, obtains diameter 50mm, the block materials of thickness 2mm.With silica as substrate, with block materials as target, pass through
The method of magnetron sputtering sputters one layer of uniform film in silicon oxide substrate, obtains final product the lithium carbon boron oxygen containing plane triangle group
Compound solid electrolyte film material.Sputter coating be in vacuum chamber ar pressure be 1Pa, radio-frequency power supply power during sputter coating
For 140W, plated film time is 2h, and thickness is 300nm.
Embodiment 14
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte film material containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 1
Li2.58C0.42B0.58O3Powder body material Jing planetary ball mill 900r/min ball milling 3h, the powder for obtaining is put in the graphite jig of diameter 30mm,
600 DEG C are risen to the speed of 5 DEG C/min in vacuum atmosphere with the pressure of 6MPa using isothermal static pressure machine, at 600 DEG C 4h is suppressed, obtained
To diameter 30mm, the block materials of thickness 2mm.With silica as substrate, with block materials as target, by the side of pulsed laser deposition
Method sputters one layer of uniform film in silicon oxide substrate, obtains final product the lithium carbon boron oxide compound solid electrolyte containing plane triangle group
Thin-film material.Optical maser wavelength is 248nm, and frequency is 5Hz, and energy density is 2J/cm2, plated film time is 4h, and thickness is 500nm.
Embodiment 15
The present embodiment prepares the lithium carbon boron oxide compound solid electrolyte film material containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3Powder body material Jing planetary ball mill 900r/min ball milling 3h, by the powder body material for obtaining and 5% poly- inclined fluorine
Ethene mixing is dissolved in appropriate 1-METHYLPYRROLIDONE, is sufficiently mixed and is obtained slurry.Using the method for spin coating, slurry is dripped in oxygen
On silicon substrate, with the rotating speed spin coating of 500r/min, it is repeated multiple times after obtain the lithium carbon boron oxide compound containing plane triangle group
Solid electrolyte film material, then 300 DEG C of annealing 1h of Jing, obtain the film that thickness is 500nm.
Embodiment 16～54
In embodiment 16～54, the lithium carbon boron oxide compound solid electrolyte Li containing plane triangle group2+xCzBbMmO3-nYn
Powder body material, block materials, the preparation method of thin-film material are identical with the method for one of them in previous embodiment, but M, Y
Element is different, and the value of x, z, b, m, n is different, and the composition and its property of various materials are as shown in table 1 in case study on implementation 9,16～54.
Table 1
Embodiment 55
The present embodiment prepares the lithium carbon boron oxide compound solid state electrolysis composite material containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3Powder body material and SiO2Powder body material, is in mass ratio 95:After 5 are well mixed, Jing high-energy ball milling 3000r/
Min ball milling 4h, obtain composite powder material of the particle diameter within 100nm.
Embodiment 56
The present embodiment prepares the lithium carbon boron oxide compound solid state electrolysis composite material containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3Powder body material Jing planetary ball mill 900r/min ball milling 3h, by the powder for obtaining the graphite of diameter 50mm is put into
In mould, 600 DEG C are risen to the speed of 5 DEG C/min in vacuum atmosphere with the pressure of 5MPa using isothermal static pressure machine, at 600 DEG C
Lower compacting 4h, obtains diameter 50mm, the block materials of thickness 2mm.Same method prepares SiO2Target.It is common using magnetron sputtering
The method of sputtering is in one layer of uniform composite film material of Pt Growns.Sputter coating is that ar pressure is in vacuum chamber
1Pa, radio-frequency power supply power is 140W during sputter coating, and plated film time is 1h, and thickness is 400nm.
Embodiment 57～76
In embodiment 57～76, the lithium carbon boron oxide compound solid electrolyte Li containing plane triangle group2+xCzBbMmO3- nYnThe preparation method of composite is identical with the method for previous embodiment 55 or 56, but M, Y element are different, x, z, b, m, n's
Value is different, and the composition and its property of various materials are as shown in table 2 in case study on implementation 55～76.
Table 2
Embodiment 77
The present embodiment prepares the lithium carbon boron oxide compound solid state electrolysis composite material containing plane triangle group to illustrate
Detailed process.
By the lithium carbon boron oxide compound solid electrolyte containing plane triangle group obtained in above-mentioned case study on implementation 9
Li2.58C0.42B0.58O3In molar ratio example is 1 to powder body material with polyethylene glycol oxide (PEO):After 20 are well mixed, N- methyl is dissolved in
In pyrrolidones (NMP), in pouring polytetrafluoro plate after stirring into, NMP is evaporated in 50 degrees Celsius of baking ovens, obtains thickness
Spend the lithium carbon boron oxide compound solid electrolyte composite material film containing plane triangle group for 100 μm.
Embodiment 78～111
In embodiment 78～111, the lithium carbon boron oxide compound solid electrolyte Li containing plane triangle group2+ xCzBbMmO3-nYnThe preparation method of composite is identical with the method for previous embodiment 77, but M, Y element are different, x, z, b, m,
The value of n is different, and the composition and its property of various materials are as shown in table 3 in case study on implementation 77.
Table 3
The lithium carbon boron oxide compound solid state electrolysis material containing plane triangle group that above-mentioned each embodiment of the present invention is provided
Material, in can be used for lithium ion battery.
Therefore, accordingly, present invention also offers a kind of lithium ion battery, comprising the lithium carbon boron oxygen described in any embodiment
Compound solid electrolyte material solid electrolyte material.
Embodiment 112
The present embodiment prepares the lithium carbon boron oxide compound solid state electrolysis composite material containing plane triangle group to illustrate
Lithium ion battery, and preparation method thereof.
The lithium ion battery of the present embodiment includes positive pole, negative pole and electrolyte.
The positive pole of above-mentioned lithium ion battery includes positive active material, and the positive active material is selected from the compound of Li,
Specifically include Lie(FeaCohMncNid)f(PO4)g、Li2e(FeaCohMncNid)f(SiO4)g、Li2e(Fe2aCo2hMn2cNi2d)f
(SO4)3g、Lie(FeaCohMncNid)f(BO3)g、Li3eV2f(PO4)3g、LieCofO2g、FefS2g、MnfO2g、Lie(NiiCojMnk)fO2g、Lie(NiaCohAlc)fO2、Li2eMnfO3g-Lie(NiiCojMnk)fO2g、Lie(NiapMnq)fO4gIn one or more；Its
Middle i+j+k=1, and 0≤i≤1,0≤j≤1,0≤k≤1, a+h+c+d=1, and 0≤a≤1,0≤h≤1,0≤c≤1,0≤
D≤1,0.5≤e≤1.5,0.5≤f≤1.5,0.5≤g≤1.5, p+q=2 and 0≤p≤2.5,0≤q≤2.5.
The negative pole of above-mentioned lithium ion battery includes negative electrode active material, and the negative electrode active material includes material with carbon element, Si materials
Material, metal Li simple substance, metal LiX alloys, wherein the material with carbon element includes graphite, hard carbon, soft carbon and its derivative, the alkali gold
In category LiX alloys, X is one or more in Sn, Si, Al, Ge, Sb, B.
Organic additive can be included in the positive pole and/or negative pole of above-mentioned lithium ion battery, the organic additive is concrete
For organic matter binding agent, selected from polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, ethylene, propylene
One or more in acid, ethylene vinyl acetate, butadiene-styrene rubber or derivatives thereof.
Inorganic additive, the inorganic additive choosing can be included in the positive pole and/or negative electrode layer of above-mentioned lithium ion battery
One or more from material with carbon element, conductive metal material, inorganic conductive material.Wherein described material with carbon element includes：Carbon nanometer, carbon
One or more in fiber, Graphene, native graphite, Delanium, hard carbon, soft carbon, conductive black, the metallic conduction material
Material includes：Metallic titanium powder, copper powder, metal nickel powder, Titanium fiber, metal copper fiber, metallic nickel fiber, metallic titanium membrane
In one or more, the inorganic conductive material includes：TiN、TaN、MoSi2In one or more.
The lithium carbon boron oxide compound solid electrolyte material Li provided comprising the present invention in above-mentioned lithium ion battery2+ xCzBbMmO3-nYn, wherein, the mass content of the inorganic solid electrolyte material is 0 ＜ x ＜ 100%.
The operating temperature of the lithium ion battery that the present invention is provided, in room temperature to 500 DEG C.Can use as one-shot battery,
Can also discharge and recharge.
Present invention also offers the preparation method of above-mentioned lithium ion battery.
In the first optional scheme, above-mentioned preparation method of lithium ion battery can be：Solid sintering technology will be without electromechanics
Solution material sinters ceramic of compact piece into, then the positive pole for preparing, cathode pole piece are attached to into the both sides of potsherd.
In second optional scheme, above-mentioned preparation method of lithium ion battery can be：Solid sintering technology will be without electromechanics
Solution material sinters ceramic of compact piece into, then prepares positive electrode and/or negative material slurry, and positive pole or/and negative pole are coated
On electrolyte ceramicses piece.
In the third optional scheme, above-mentioned preparation method of lithium ion battery can be：Solid sintering technology will be without electromechanics
Solution material sinters ceramic of compact piece into, then positive pole or/and negative pole are combined by solid sintering technology with electrolyte ceramicses piece.
In the 4th kind of optional scheme, above-mentioned preparation method of lithium ion battery can be：Solid sintering technology will be without electromechanics
Solution material sinters ceramic of compact piece into, reuses magnetron sputtering, pulsed laser deposition, ald, thermal evaporation, electron beam
The methods such as evaporation, vapour deposition are combined positive pole or/and negative pole with electrolyte ceramicses piece.
In the 5th kind of optional scheme, above-mentioned preparation method of lithium ion battery can be：Using the method for preparing film
Positive pole, inorganic electrolyte material and negative pole are prepared into into the hull cell of sandwich structure.
It is following that the concrete of lithium ion battery is prepared using method provided in an embodiment of the present invention with the explanation of multiple instantiations
Process and battery behavior.
Embodiment 113
The implementation case contains the preparation method of the solid state battery of above-mentioned solid electrolyte material to illustrate the present invention.This reality
Example is applied there is provided a kind of solid lithium ion battery of the wide electrochemical window that can be worked within the scope of wide temperature.The structure of battery
Into including：Anode layer, dielectric substrate, negative electrode layer.
Anode layer includes in the implementation case：It is positive active material, positive pole inorganic additive, positive pole organic additive, solid
State electrolyte.Positive active material is LiCoO2, mass fraction is 60%.Positive pole inorganic additive is conductive black, and quality is divided
Number is 5%.Positive pole organic additive is PVDF, and mass fraction is 5%, and solid electrolyte is to prepare in above-described embodiment
Li2.58C0.42B0.58O3, mass fraction is 30%.Dielectric substrate is the Li prepared in above-described embodiment2.58C0.42B0.58O3.Negative pole
Layer includes：Negative electrode active material, negative pole inorganic additive, negative pole organic additive, solid electrolyte.Negative electrode active material is behaved
Graphite is made, mass fraction is 60%.Negative pole inorganic additive is acetylene black (AB), and mass fraction is 5%.Negative pole organic additive
For PVDF, mass fraction is 5%, and solid electrolyte is Li prepared by above-described embodiment2.58C0.42B0.58O3, mass fraction is
30%.
Anode layer electrode piece preparation method：Solvent is done using polypyrrole alkanone (NMP), the positive pole of proportioning as implied above is lived
Property material LiCoO2, inorganic additive, organic additive, solid electrolyte be mixed into uniform sizing material, be evenly applied on aluminium foil,
Drying obtains anode layer electrode slice.
Negative electrode layer electrode piece preparation method：Solvent is done using polypyrrole alkanone (NMP), the negative pole of proportioning as implied above is lived
Property material Delanium, inorganic additive, organic additive, solid electrolyte are mixed into uniform sizing material, are evenly applied to Copper Foil
On, drying obtains negative electrode layer electrode slice.
The preparation method of dielectric substrate：The Li obtained in embodiment 12.58C0.42B0.58O3Powder is put into diameter 13mm not
In rust steel mold, after being taken out with the pressure of 6MPa pressure 2min in Muffle furnace with the ramp of 3 DEG C/min to 650 DEG C, insulation
Room temperature taking-up is down to after 2h, diameter 13mm, the fine and close solid electrolyte potsherd of thickness 0.3mm is obtained.
Battery preparation technique：Preparation anode layer electrode slice as implied above, solid electrolyte potsherd, negative electrode layer electrode slice,
Then three stackings are put, in being fitted into battery case.
The battery C1 that the present embodiment is obtained, the temperature range for being capable of normal work is 20～250 DEG C, charging/discharging voltage scope
For 3.7～4.5V.
Embodiment 114
The implementation case contains the preparation method of the solid state battery of above-mentioned solid electrolyte material to illustrate the present invention.This reality
Example is applied there is provided a kind of solid lithium ion battery of the wide electrochemical window that can be worked within the scope of wide temperature.The structure of battery
Into including：Anode layer, dielectric substrate, negative electrode layer.
Anode layer includes in the implementation case：It is positive active material, positive pole inorganic additive, positive pole organic additive, solid
State electrolyte.Positive active material is LiCoO2, mass fraction is 60%.Positive pole inorganic additive is conductive black, and quality is divided
Number is 5%.Positive pole organic additive is PVDF, and mass fraction is 5%, and solid electrolyte is prepared by above-described embodiment
Li2.58C0.42B0.58O3, mass fraction is 30%.Dielectric substrate is the Li prepared in above-described embodiment2.58C0.42B0.58O3.Negative pole
Layer includes：Negative electrode active material, negative pole inorganic additive, negative pole organic additive, solid electrolyte.Negative electrode active material is behaved
Graphite is made, mass fraction is 60%.Negative pole inorganic additive is acetylene black (AB), and mass fraction is 5%.Negative pole organic additive
For PVDF, mass fraction is 5%, and solid electrolyte is Li prepared by above-described embodiment2.58C0.42B0.58O3, mass fraction is
30%.
Anode layer preparation method：Solvent is done using polypyrrole alkanone (NMP), by the positive active material of proportioning as implied above
LiCoO2, inorganic additive, organic additive, solid electrolyte be mixed into uniform sizing material.
Negative electrode layer preparation method：Solvent is done using polypyrrole alkanone (NMP), by the negative electrode active material of proportioning as implied above
Delanium, inorganic additive, organic additive, solid electrolyte are mixed into uniform sizing material.
The preparation method of dielectric substrate：The Li obtained in embodiment 12.58C0.42B0.58O3Powder is put into diameter 13mm not
In rust steel mold, after being taken out with the pressure of 6MPa pressure 2min in Muffle furnace with the ramp of 3 DEG C/min to 650 DEG C, insulation
Room temperature taking-up is down to after 2h, diameter 13mm, the fine and close solid electrolyte potsherd of thickness 0.3mm is obtained.
Battery preparation technique：The positive pole cathode size of preparation as implied above is respectively coated on the two of solid electrolyte potsherd
Side, dries under infrared lamp, then sputters golden collector in positive pole negative pole both sides using ion sputtering instrument.
The battery C2 that the present embodiment is obtained, the temperature range for being capable of normal work is 20～250 DEG C, charging/discharging voltage scope
For 3.0～4.5V.
Embodiment 115
The implementation case contains the preparation method of the solid state battery of above-mentioned solid electrolyte material to illustrate the present invention.This reality
Example is applied there is provided a kind of solid lithium ion battery of the wide electrochemical window that can be worked within the scope of wide temperature.The structure of battery
Into including：Anode layer, dielectric substrate, negative electrode layer.
Anode layer includes in the implementation case：It is positive active material, positive pole inorganic additive, positive pole organic additive, solid
State electrolyte.Positive active material is LiCoO2, mass fraction is 60%.Positive pole inorganic additive is TiN, and mass fraction is
5%.Positive pole organic additive is PVDF, and mass fraction is 5%.Solid electrolyte is prepared by above-described embodiment
Li2.58C0.42B0.58O3, mass fraction is 30%.Dielectric substrate is the Li prepared in above-described embodiment2.58C0.42B0.58O3.Negative pole
Layer includes：Negative electrode active material, negative pole inorganic additive, solid electrolyte.Negative electrode active material is Si, and mass fraction is
65%.Negative pole inorganic additive is TiN, and mass fraction is 5%.Negative pole organic additive is PVDF, and mass fraction is 5%, Gu
State electrolyte is Li prepared by above-described embodiment2.58C0.42B0.58O3, mass fraction is 30%.
Anode layer preparation method：Solvent is done using polypyrrole alkanone (NMP), by the positive active material of proportioning as implied above
LiCoO2, inorganic additive, organic additive, solid electrolyte be mixed into uniform sizing material.
Negative electrode layer preparation method：Solvent is done using polypyrrole alkanone (NMP), by the negative electrode active material of proportioning as implied above
Si, inorganic additive, organic additive, solid electrolyte are mixed into uniform sizing material.
The preparation method of dielectric substrate：The Li obtained in embodiment 12.58C0.42B0.58O3Powder is put into diameter 13mm not
In rust steel mold, after being taken out with the pressure of 6MPa pressure 2min in Muffle furnace with the ramp of 3 DEG C/min to 650 DEG C, insulation
Room temperature taking-up is down to after 2h, diameter 13mm, the fine and close solid electrolyte potsherd of thickness 0.3mm is obtained.
Battery preparation technique：The positive pole cathode size of preparation as implied above is respectively coated on the two of solid electrolyte potsherd
Side, dries under infrared lamp, is then warming up to 500 DEG C with 3 DEG C/min in tube furnace Ar gas atmosphere, is incubated 1h, is down to room temperature and takes
Go out.Then golden collector is sputtered in positive pole negative pole both sides using ion sputtering instrument.
The battery C3 that the present embodiment is obtained, the temperature range for being capable of normal work is 20～250 DEG C, charging/discharging voltage scope
For 3.0～4.5V.
Embodiment 116
The implementation case contains the preparation method of the solid state battery of above-mentioned solid electrolyte material to illustrate the present invention.This reality
Example is applied there is provided a kind of solid lithium ion battery of the wide electrochemical window that can be worked within the scope of wide temperature.The structure of battery
Into including：Anode layer, dielectric substrate, negative electrode layer.
Anode layer includes in the implementation case：Positive active material, positive pole inorganic additive, solid electrolyte.Positive pole is lived
Property material be LiCoO2, mass fraction is 65%.Positive pole inorganic additive is TiN, and mass fraction is 5%.Solid electrolyte is
Li prepared by above-described embodiment2.58C0.42B0.58O3, mass fraction is 30%.Dielectric substrate is to prepare in above-described embodiment
Li2.58C0.42B0.58O3.Negative electrode layer includes：Negative electrode active material, negative pole inorganic additive, solid electrolyte.Negative electrode active material
For Si, mass fraction is 65%.Negative pole inorganic additive is TiN, and mass fraction is 5%.Solid electrolyte is above-described embodiment
The Li of preparation2.58C0.42B0.58O3, mass fraction is 30%.
Anode layer preparation method：By positive active material LiCoO2, inorganic additive, the solid state electrolysis of ratio as implied above
Material is sufficiently mixed uniformly.
Negative electrode layer preparation method：By the negative electrode active material Si of ratio as implied above, inorganic additive, solid state electrolysis material
Material is sufficiently mixed uniform.
Battery preparation technique：By above-mentioned anode layer powder, solid electrolyte powder, negative electrode layer powder in order in layer
Be put into it is compressing in the stainless compression molds of diameter 13mm, after taking-up in tube furnace Ar gas atmosphere with 3 DEG C/min intensification
To 500 DEG C, 1h is incubated, is down to room temperature taking-up.Then golden collector is sputtered in positive pole negative pole both sides using ion sputtering instrument.
The battery C4 that the present embodiment is obtained, the temperature range for being capable of normal work is 20～250 DEG C, charging/discharging voltage scope
For 3.7～4.2V.
Embodiment 117
The implementation case contains the preparation method of the solid state battery of above-mentioned solid electrolyte material to illustrate the present invention.This reality
Example is applied there is provided a kind of solid lithium ion battery of the wide electrochemical window that can be worked within the scope of wide temperature.The structure of battery
Into including：Anode layer, dielectric substrate, negative electrode layer.
The preparation method of dielectric substrate：The Li obtained in embodiment 12.58C0.42B0.58O3Powder is put into diameter 13mm not
In rust steel mold, after being taken out with the pressure of 6MPa pressure 2min in Muffle furnace with the ramp of 3 DEG C/min to 650 DEG C, insulation
Room temperature taking-up is down to after 2h, diameter 13mm, the fine and close solid electrolyte potsherd of thickness 0.3mm is obtained.
It is raw under method room temperature of the side with pulsed laser deposition (PLD) with above-mentioned solid electrolyte potsherd as substrate
Long one layer of LiCoO2, target is the Li of polycrystalline1.2CoO2, positive pole thickness is about 200nm.Then with the method sputtering one of ion sputtering
The golden collector of layer.Opposite side is deposited with layer of metal Li with the method for vacuum thermal evaporation (VTE), and thickness is about 500nm, then with from
The method of son sputtering sputters one layer of golden collector.
The battery C5 that the present embodiment is obtained, the temperature range for being capable of normal work is 20～150 DEG C, and charging/discharging voltage is 3-
4.5V。
Embodiment 118
The implementation case contains the preparation method of the solid state battery of above-mentioned solid electrolyte material to illustrate the present invention.This reality
Example is applied there is provided a kind of solid lithium ion battery of the wide electrochemical window that can be worked within the scope of wide temperature.The structure of battery
Into including：Anode layer, dielectric substrate, negative electrode layer.
Anode layer, dielectric substrate, the negative electrode layer of battery is in layer grown using the method for film preparation, obtains one
Hull cell.Positive electrode Li1.2CoO2, electrolyte Li2.58C0.42B0.58O3It is pressed into target.With goldleaf as substrate, with arteries and veins
One layer of LiCoO is grown under the method room temperature of impulse light deposition (PLD)2, thickness is about 200nm, then again with the side of magnetron sputtering
Method grows one layer of solid electrolyte film, and thickness is about 2 μm, then again with method one layer of gold of evaporation of vacuum thermal evaporation (VTE)
Category Li, thickness is about 500nm, finally sputters one layer of golden collector with the method for ion sputtering.
The battery C6 that the present embodiment is obtained, the temperature range for being capable of normal work is 20～150 DEG C, and charging/discharging voltage is 3-
4.5V。
119～embodiment of embodiment 143
119～embodiment of embodiment 143 provide it is various can wide temperature range work with wide electrochemical window
The solid lithium ion battery of mouth.Battery numbering is C7～C31, its positive pole or/and negative pole or/and electrolyte preparation technology with implement
The preparation method of one is identical in example 113～118, and simply the positive and negative pole material of battery is different from electrolyte.Each battery
Anode layer, negative electrode layer and dielectric substrate composition it is as shown in table 4.
Table 4
The operating temperature and charging/discharging voltage scope of battery C7～C31 are as shown in table 5 below in embodiment 113～118.
Table 5
Embodiments provide a kind of lithium carbon boron oxide compound solid electrolyte material with plane triangle group
And battery, with electrochemical stability, chemical stability, storage stability, high-temperature stability, relatively low electronic conductivity,
There is higher ionic conductivity under high temperature.Can be in wide temperature using the lithium ion battery of the solid electrolyte material of the present invention
Work under degree scope, particularly work at high temperature, can be used as one-shot battery, it is also possible to use as secondary cell.With this
Solid electrolyte material is the lithium ion battery of electrolyte, due to not containing organic electrolyte, and fundamentally solves current business
With the safety issue of lithium ion battery.
Above-described specific embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that the specific embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc. all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of lithium carbon boron oxide compound solid electrolyte material containing plane triangle group, it is characterised in that the material
Chemical general formula is：Li2+xCzBbMmO3-nYn；
Wherein, each C or B or M and adjacent three O constitutes a plane triangle structure, or each C or B or M with it is adjacent
Three Y constitute a plane triangle structure；M is to be doped substituted element to Li or C or B；Y is that O is doped
Substituted element；The M is specially Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, one or more in Zr；The Y is concrete
For S, N, one or more in F；The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤1,0.3
≤ z≤1,0≤b≤1,0≤m≤0.2,0≤n≤0.5, and m, n are zero when different；The proterties of the material is：Powder body material,
Any one in block materials, thin-film material or composite.
2. the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group according to claim 1, its feature
It is, in Raman spectrum, in 700cm-1Above 1200cm-1Region below has peak；In infrared spectrum, in 750cm-1More than
1500cm-1Region below has peak.
3. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is powder body material, methods described includes：
By Li sources, C sources, B sources, M sources, Y sources according to Li2+xCzBbMmO3-nYnMolar ratio ingredient, forms presoma；The M is specially
One or more in Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, Zr；The Y is specially S, N, one or more in F；
The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤1,0.3≤z≤1,0≤b≤1,0≤m≤
0.2,0≤n≤0.5, and m, n are zero when different；
Handle mill or planetary ball mill or high-energy ball milling is well mixed, obtain precursor powder；
The precursor powder is pre-processed 1～12 hour in 100 DEG C～500 DEG C air atmospheres；
Precursor powder after heat treatment is carried out again hand mill or planetary ball mill or high-energy ball milling；
Sinter 24～336 hours at 500 DEG C～650 DEG C, that is, obtain the powder body material.
4. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is powder body material, methods described includes：
By Li sources, C sources, B sources, M sources, Y sources according to Li2+xCzBbMmO3-nYnMolar ratio ingredient, forms presoma；The M is specially
One or more in Na, K, Mg, Ca, Al, Ga, La, Y, Si, Ge, Zr；The Y is specially S, N, one or more in F；
The x, z, b, m, n are respectively the molar percentage shared by corresponding element；0≤x≤1,0.3≤z≤1,0≤b≤1,0≤m≤
0.2,0≤n≤0.5, and m, n are zero when different；
Handle mill or planetary ball mill or high-energy ball milling is well mixed, obtain precursor powder；
The precursor powder is pre-processed 1～12 hour in 100 DEG C～500 DEG C air atmospheres；
Precursor powder after heat treatment is carried out again hand mill or planetary ball mill or high-energy ball milling；
Sinter 1～24 hour at 500 DEG C～650 DEG C, then carry out hand mill or planetary ball mill or high-energy ball milling；
Sinter 1～24 hour at 500 DEG C～650 DEG C again, that is, obtain the powder body material.
5. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is block materials, methods described includes：
After the powder body material mechanical compression molding that the claims 3 or 4 are prepared, at 500 DEG C～650 DEG C 6 are re-sintered
～12 hours, obtain the block materials.
6. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is block materials, methods described includes：
The powder body material that the claims 3 or 4 are prepared is put into into compression mold, using the method for isothermal static pressure, 500
DEG C～650 DEG C, suppress 2～6 hours under 1MPa～6MPa, obtain the block materials.
7. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is block materials, methods described includes：
After the powder body material melting that the claims 3 or 4 are prepared, in pouring mould into, cooling obtains the block material
Material.
8. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is thin-film material, methods described includes：
The powder body material that the claims 3 or 4 are prepared is pressed under conditions of 3MPa～500MPa, 500 DEG C～650 DEG C
Dense target material is made, institute is prepared by any one of magnetron sputtering, pulsed laser deposition, thermal evaporation or electron beam evaporation
State thin-film material.
9. a kind of preparation of the lithium carbon boron oxide compound solid electrolyte material containing plane triangle group as claimed in claim 1
Method, it is characterised in that the material is composite, methods described includes：
The powder body material that the claims 3 or 4 are prepared is combined with inorganic material, or powder body material, inorganic material
Material and organic material are combined, and obtain the composite；
Wherein, the inorganic material includes SiO2、Al2O3Or compound containing Li；The organic material include polyethylene glycol oxide PEO,
One or more mixing in Kynoar PVDF, polyacrylonitrile (PAN), polymethyl methacrylate MMA.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery include described in the claims 1 or 2 containing flat
The lithium carbon boron oxide compound solid electrolyte material of face triangle group.
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| CN105576289A (en) * | 2016-02-05 | 2016-05-11 | 中国科学院西安光学精密机械研究所 | F-And N3+Ion-synergistically-doped lithium ion solid electrolyte and preparation method thereof |
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