CN108155413A - The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method - Google Patents
The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method Download PDFInfo
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- 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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
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- H01M2300/0068—Solid electrolytes inorganic
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- Y02E60/10—Energy storage using batteries
Abstract
The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method belong to electrolyte field.Stoichiometric equation is Li7‑y+xLa3‑xAxZr2‑yTayO12.Wherein, A represents one kind in doped chemical Sr, Ba, meets 0 ＜ y ＜, 2,0 ＜ x ＜ y.The purpose of Zr doping Ta is the cubic phase of stabilizing material, improves material ions conductivity；The purpose of La doping divalent alkaline-earth metals is to increase carrier concentration.Using element radius and the discrepancy adjustment crystal structure of bond valence, the transmission channel more suitable for lithium ion conduction is formed, reduces lithium ion mobility activation energy, improves ionic conductivity, while is reduced into phase temperature, acceleration of sintering, improves material density etc..Li with stable cubic phase structure is obtained by codope7La3Zr2O12Based solid electrolyte material, material show good sintering character, low lithium ion mobility activation energy, high ionic conductivity simultaneously, have important application value.
Description
Technical field
The invention belongs to new materials and electrochemical field, and in particular to the lithium of a kind of divalent alkaline-earth metal and tantalum codope from
Son conduction Li7La3Zr2O12Solid electrolyte material and preparation method thereof.
Technical background
The prehuman energy system of mesh is mainly made of fossil fuel, nuclear energy and regenerative resource.Fossil fuel is mesh
The preceding the most widely used energy, however bring the problem of very big while fossil fuel large-scale use：On the one hand they
Formation in the earth's crust needs tens of million years, and the consumption of its reserves is very rapid；Another aspect fossil fuel makes
The problems such as with can inevitably bring environmental pollution and greenhouse effects.Water energy, wind energy, solar energy, geothermal energy and tide
Energy etc. is that environmentally protective regenerative resource the most rapid is compared in development since the 21th century, but present in these energy
Generate electricity unstability, intermittence so that these generations of electricity by new energy are unable to direct grid-connected, and high-efficiency energy-storage becomes the weight of new energy development
In it is weight.
Electrochemical cell becomes the outstanding person in various energy-storage systems since its is efficient, response is fast.All by people
In widely known battery, there are highest volume and weight energy densities for lithium ion battery.Lithium ion battery also has simultaneously
It has extended cycle life, environmental pollution is small, memory-less effect.Nowadays this, which makes it, increases most fast and most promising electricity
Pool technology is widely used in low-power consumption and high-power electronic equipment, such as mobile phone, laptop, electric tool, and positive
Electric vehicle application development.However, the electrolyte of most of lithium ion batteries used now is all liquid organic system, and have
Machine electrolyte has that leakage burn into is inflammable, the safety issues such as explosive.Moreover, use lithium metal conduct to improve energy density
During electrode, Li dendrite can be generated, penetrates liquid electrolyte, easily caused the short circuit of battery, cause safety problem.Liquid electrolyte
Voltage window also limit the development and application of high-voltage anode material, affect the development of high energy density cells.It is inorganic
Solid electrolyte can be solved the problems, such as existing for liquid electrolyte liquid system mentioned above.Therefore exploitation have high thermodynamic and
The inorganic solid electrolyte of chemical stabilization and high ionic conductivity becomes an important directions in current battery field.
Ideal solid electrolyte needs to meet following key request：(1) lithium ion conductivity is high, meanwhile, lithium from
Sub- transport number is close to 1；(2) electrochemical window range is big, and there are one high electrochemical decomposition voltages (relative to Li for tool+/ Li), with
Use the positive electrode of high voltage；(3) chemical stability is good.Lithium battery manufacture and operational process in, not with anode and cathode
Any reaction, which occurs, to be caused to generate side reaction product at electrode and electrolyte interface；(4) electric charge transfer between electrode and electrolyte
Resistance is small；(5) preparation method simple economy, it is environmental-friendly.
The solid electrolyte developed at present mainly has following a few major class：LISICON types, argyrodite type, NASICON types,
Ca-Ti ore type, carbuncle type.They respectively have advantage and disadvantage.LISICON types and thio LISICON types compound structure are similar to orthogonal
Crystallographic system and space group are Pnma's-Li3PO4Structure, wherein, Li10MP2S12(M=Si, Ge, Sn) and Li11Si2PS12With most
High room temperature lithium ion conductivity, higher than 10-2S/cm.But when contacting lithium, Li10GeP2S12It has been found that be it is unstable, together
When, sulfur-containing compound have hygroscopicity, with water occur fast reaction the shortcomings that, be not easy to prepare and store in air.According to
The report of Deiseroth et al., lithium argyrodite Li6PS5X (X=Cl, Br or I) is newfound fast lithium ion conductor, room
Warm conductivity is 7 × 10-3S/cm.Preliminary test shows Li6PS5The electrochemical window of X (X=Cl, Br or I) it is very wide (0V~
7V).However, it is there is also hygroscopicity, the problem of reaction with water, it is difficult to operate in air.NASICON types solid electrolyte rises
Derived from sodium ion electrolyte, NASICON sodium ion electrolytes are a kind of zirconium phosphate of non-stoichiometric, are between NaZr2
(PO4)3With Na4Zr2(SiO4)3Between solid solution.The commercial lithium ion solid electrolyte with NASICON structures in the market
Li1.3Al0.3Ti1.7(PO4)3, lithium ion conductivity is 10-4More than S/cm, but when lithium metal is used to do electrode, Ti4+Easily gone back
Original is into Ti3+, and then electronic conductance is generated, the transference number of ions of electrolyte is influenced, limits Li1.3Al0.3Ti1.7(PO4)3Make
Use range.And to LiZr2(PO4)3Solid electrolyte, due to the stability of zirconium ion and phosphate anion, LiZr2(PO4)3As
Solid electrolyte is a relatively good selection in lithium battery, but it is at room temperature three monoclinic phases, and lithium ion conductivity is low.Calcium
Perovskite like structure composition is ABO3, the anion frame in crystal is by BO6Octahedron composition, cube vertex position are accounted for by A cations
It is full.Ca-Ti ore type lithium ion solid electrolyte is mainly based on the electrolyte using Ti as matrix at present, such as Li3xLn2/3-xTiO3, Ln
=La.But contained Ti in the system4+It can be made to react with metal lithium electrode, there is also Ti4+It is reduced into Ti3+Ask
Topic.
Since the material of sulfur-bearing and titaniferous is limited by chemical stability and electrochemical stability, it is difficult to it is practical,
The ionic conductivity of his material is again relatively low, it is difficult to meet the requirement of current lithium battery.So just from the point of view of current research, stone
Garnet type solid electrolyte is the solid electrolyte for most having Commercial Prospect.Preferably the chemical general formula of garnet type structure is
A3B2C3O12, crystal structure is the structure of face-centered cubic packing, space group Ia-3d.O'Callaghan etc. has studied stone at first
The solid electrolytic material Li of garnet type structure3Ln3Te2O12In (Ln=Y, Pr, Nd, Sm-Lu) lithium ion position occupy with lithium from
Relationship between electron conductivity.Thangadurai in 2003 etc. reports space group as Ia-3d garnet type structures
Li5La3M2O12(M=Nb, Ta), room-temperature conductivity 10-6S/cm, activation can be less than 0.5eV.In 2007, Murugan etc.
It has synthesized with higher room-temperature conductivity (10-4S/cm the carbuncle type Li of cubic phase crystal structure)7La3Zr2O12(space group
For Ia-3d), it is determined that each chemical formula can accommodate 7 Li ions in garnet type structure.Li7La3Zr2O12Have cubic and vertical
The two kinds of crystal structures in side.Wherein, La is 8 coordinations, and Zr is 6 coordinations, is shared by side and connects into main body frame, lithium ion is being formed
Channel in move.And the difference of four directions and cube both structures position that mainly lithium ion occupies is different.
Li7La3Zr2O12Cubic phase and tetragonal phase structure it was found that, the lithium ion conductivity of cubic phase is than four at a lower temperature
The high 1-2 order of magnitude of square phase.This species diversity may be always to be ordered into because of the lithium ion in tetragonal phase structure and vacancy, and
In cubic phase crystal structure, the arrangement of these positions is unordered, and cubic phase crystal structure symmetry is also better than four directions
Phase structure.
There are many advantages, such as chemical stability compared to other kinds of solid electrolyte for garnet-type solid electrolyte
Good, good, electrochemical window mouth width of electrochemical stability etc., but there is also many problems.First, traditional liquid electrolyte is at room temperature
Conductivity is 10-2The S/cm orders of magnitude, and the garnet-type solid electrolyte conductivity at room temperature reported at present is much lower.The
Two, heat treatment temperature is higher in the pure phase preparation process of garnet-type solid electrolyte, and cost is higher, and preparation process is complicated.The
Three, in its practical application, need compression molding high temperature sintering fine and close, and lithium is easily volatilized in the form of lithia under high temperature,
Therefore it is densified under the premise of pure phase is kept difficult.
Doping is a kind of effective ways for improving solid electrolyte conductivity, and part substitution, profit are carried out using aliovalent element
With element radius and the discrepancy adjustment crystal structure of bond valence, the transmission channel more suitable for lithium ion conduction is formed, is conducive to lithium
Ion transfer improves lithium ion conductivity, while promotes the formation of material pure phase and the densification of material.
Invention content
The present invention provides the Li of a kind of divalent alkaline-earth metal and tantalum codope for existing technical background7La3Zr2O12
Solid electrolyte material and preparation method thereof.Technical solution is as follows：
In a first aspect, the present invention provides a kind of divalent alkaline-earth metals and the Li of tantalum codope7La3Zr2O12Solid electrolyte
Material, the Zr purposes for mixing Ta are stable cubic phase structures, improve ionic conductivity.La are adulterated the main of divalent alkaline-earth metal
Purpose is fine tuning lithium concentration, reaches highest lithium ion conductivity, while utilize the discrepancy adjustment of element radius and bond valence
Crystal structure forms the transmission channel more suitable for lithium ion conduction, reduces lithium ion mobility activation energy, improves lithium ion conductance
Rate, and promote the material into mutually and densified sintering product.
A kind of Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material, it is characterised in that chemistry meter
Amount formula is Li7-y+xLa3-xAxZr2-yTayO12, wherein, A represents one kind in doped chemical Sr, Ba, meets 0 ＜ y ＜, 2,0 ＜ x ＜
Y, undoped Li7La3Zr2O12Material is tetragonal phase, and mixing Ta by Zr makes its stable structure in cubic phase.
Preferably, the doping of Ta ranging from 0.4 ＜ y ＜ 0.8.
Due to the Li of high conductivity7La3Zr2O12Material needs to have certain lithium vacancy concentration, therefore divalent alkaline-earth metal
Adulterate ranging from 0 ＜ x ＜ y.
While stable cubic phase, divalent alkaline-earth metal element is adulterated at La, it is dense that adjusting lithium ion can not only be reached
The purpose of degree, simultaneously, moreover it is possible to reduce into phase temperature, acceleration of sintering improves material density；The ionic radius of Sr and Ba is much larger than
The ionic radius of LaTherefore lattice can also be expanded by mixing Sr and Ba, so as to adjust lithium ion mobility channel sized.
Second aspect, an embodiment of the present invention provides the preparation method of the material, including：
The method for preparing the material is as follows：By Li source compound, lanthanum source compound, divalent alkaline-earth metal compound, zirconium source
Compound and tantalum source compound are 7-y+x according to each element molar ratio:3-x:x:2-y:The ratio ball milling mixing of y is uniform, passes through
Tentatively into phase, tabletting sintering obtains the solid electrolyte material for heat treatment early period, wherein, 0 ＜ y ＜, 2,0 ＜ x ＜ y.For
Make up the volatilization loss of lithium source in sintering process, lithium source excessive 5%~20% during raw material proportioning.
Preferably, the lithium source is excessively 10%.
Preferably, the ball milling condition is 300r/min ball millings 12h.
Preferably, the heat treatment condition is 700 DEG C~950 DEG C processing 12h.
Preferably, the sintering processing is microwave sintering, and 3h is sintered at 1000 DEG C~1300 DEG C.
Li provided by the invention7La3Zr2O12Solid electrolyte material is passed through by Zr stably-doped cube phase structures
La doping divalent alkaline-earth metals have finely tuned lithium concentration, while utilize the discrepancy adjustment crystal knot of element radius and bond valence
Structure forms the transmission channel more suitable for lithium ion conduction, reduces lithium ion mobility activation energy, improves its conductivity, and
Promote the material into mutually and densified sintering product.
Description of the drawings
Fig. 1 is the Arrhenius curves and its activation energy of embodiment 1.
Fig. 2 is the Arrhenius curves and its activation energy of embodiment 2.
Fig. 3 is the Arrhenius curves and its activation energy of embodiment 3.
Fig. 4 is heat-treated tentatively for embodiment 4 into the XRD diagram of phase.
Specific embodiment
The Li of a kind of divalent alkaline-earth metal and tantalum codope provided in an embodiment of the present invention7La3Zr2O12Solid electrolytic material
Material, specific embodiment are as follows：
(1) raw material mixes
By Li source compound, lanthanum source compound, divalent alkaline-earth metal compound, zirconium source compound and tantalum source compound according to
Each element molar ratio is 7-y+x:3-x:x:2-y:The ratio of y is uniformly mixed.Wherein, 0 ＜ y ＜, 2,0 ＜ x ＜ y burn to make up
The volatilization loss of lithium source during knot, lithium source excessive 5%~20% during raw material proportioning, preferably 10%.Hybrid mode is ball milling, ball
Grinding media can be the organic solvents such as ethyl alcohol, isopropanol, wherein it is preferred that isopropanol, sphere can be agate ball, zirconium ball etc., wherein
It is preferred that zirconium ball.It is taken out after ball milling and processing is dried.
Used raw material, can buy or make by oneself on the market in the materials process is prepared, and not do herein specific
It limits.
(2) it is heat-treated
The step is to decompose the metal salt in raw material, and tentatively lithium is made to enter in lattice into phase, after reducing
Lithium volatilization in continuous sintering process.The heat-treatment temperature range of the material is 600 DEG C~950 DEG C, processing time in 6h~15h,
It is preferred that 12h.The range for selecting this heat treatment temperature be because too low temperature can not be such that metal salt decomposes and tentatively into phase,
Excessively high temperature can lead to lithium volatilization seriously and there are dephasigns.
(3) it is sintered
The raw material that above-mentioned steps are obtained adds binding agent, and compression molding carries out microwave sintering, and sintering temperature is at 1000 DEG C
~1300 DEG C, sintering time 3h.Microwave sintering has the advantages of sintering time is short, efficient, step is simple.According to common
Sintering processing, such as Muffle furnace need to increase by a step ball milling before sintering, and to improve the activity of powder, and sintering time is remote
More than 3h.
It should be noted that it is above-mentioned weigh, ball milling, drying, tabletting, the operations such as sintering are technology hand commonly used in the art
Section, those skilled in the art can be operated, no longer be illustrated herein according to actual needs.
With reference to embodiment, the present invention will be further described, but is not limited to protection scope of the present invention：
Embodiment 1：Prepare Li6.5La2.9Sr0.1Zr1.4Ta0.6O12Codope solid electrolyte material
It is 6.5 according to Li, La, Sr, Zr, Ta molar ratio:2.9:0.1:1.4:0.6 ratio weighs 1.321 grams of lithium carbonate,
2.362 grams of lanthana, 0.074 gram of strontium carbonate, 0.863 gram of zirconium oxide, 0.663 gram of tantalum oxide, wherein lithium carbonate excessive 10%.So
The ball milling 12h in isopropanol medium afterwards, ball milling speed be 300 revs/min, after processing is dried.It is heat-treated at 850 DEG C
After 12h, sheetmolding is pushed in the pressure of 300MPa, then 3h is handled at 1100 DEG C, obtains provided by the invention
Li6.5La2.9Sr0.1Zr1.4Ta0.6O12Codope solid electrolyte material.The material lithium ion migrates activation energy as 0.456eV, and 25
All-in resistance at DEG C is 139.8 Ω, radius 0.6175cm, thickness 0.05cm, and conductivity is 2.99 × 10-4S/cm, 100 DEG C
Under all-in resistance for 4.695 Ω, conductivity is 8.89 × 10-3S/cm, than non-co-doped material Li6.5La3Zr1.4Ta0.6O12Material
(4.88×10-3S/cm it is) high by about one time, while illustrating that codope stabilizes cubic phase, lithium concentration is improved, so as to
Improve lithium ion conductivity.
Embodiment 2：Prepare Li6.6La2.6Sr0.4Zr1.2Ta0.8O12Codope solid electrolyte material
It is 6.6 according to Li, La, Sr, Zr, Ta molar ratio:2.6:0.4:1.2:0.8 ratio weighs 1.341 grams of lithium carbonate,
2.118 grams of lanthana, 0.295 gram of strontium carbonate, 0.739 gram of zirconium oxide, 0.884 gram of tantalum oxide, wherein lithium carbonate excessive 10%.So
The ball milling 12h in isopropanol medium afterwards, ball milling speed be 300 revs/min, after processing is dried.It is heat-treated at 850 DEG C
After 12h, sheetmolding is pushed in the pressure of 300MPa, then 3h is handled at 1100 DEG C, obtains provided by the invention
Li6.6La2.6Sr0.4Zr1.2Ta0.8O12Codope solid electrolyte material.The material lithium ion migrates activation energy as 0.379eV, and 25
All-in resistance at DEG C is 155.3 Ω, radius 0.6165cm, thickness 0.06cm, and conductivity is 3.21 × 10-4S/cm, explanation
While codope stabilizes cubic phase, lithium concentration is improved, so as to improve lithium ion conductivity, and expands crystalline substance
Lattice reduce lithium ion mobility activation energy.
Embodiment 3：Prepare Li6.5La2.9Ba0.1Zr1.4Ta0.6O12Codope solid electrolyte material
It is 6.5 according to Li, La, Ba, Zr, Ta molar ratio:2.9:0.1:1.4:0.6 ratio weighs 1.321 grams of lithium carbonate,
2.362 grams of lanthana, 0.1 gram of barium carbonate, 0.863 gram of zirconium oxide, 0.663 gram of tantalum oxide, wherein lithium carbonate excessive 10%.Then
The ball milling 12h in isopropanol medium, ball milling speed be 300 revs/min, after processing is dried.12h is heat-treated at 800 DEG C
Afterwards, sheetmolding is pushed in the pressure of 300MPa, then handles 3h at 1050 DEG C, obtain provided by the invention
Li6.5La2.9Ba0.1Zr1.4Ta0.6O12Codope solid electrolyte material.All-in resistance at 25 DEG C is 168.9 Ω, and radius is
0.6215cm, thickness 0.044cm, conductivity are 2.15 × 10-4S/cm.The lithium ion mobility activation energy of the material is
0.325eV less than the activation energy of most of this kind of material, illustrates that codope in stable cubic phase, adjusts the same of lithium concentration
When, expand lattice, so as to adjust lithium ion mobility channel sized, reduce lithium ion mobility activation energy.
Embodiment 4：Phase temperature is reduced into while codope stable cubic phase
Li is prepared in above-mentioned identical method7La3Zr2O12, Li6.4La3Zr1.4Ta0.6O12,
Li6.5La2.9Sr0.1Zr1.4Ta0.6O12And Li6.5La2.9Ba0.1Zr1.4Ta0.6O12, increase with Sr, Ba atomic radius of codope
Greatly, it under the conditions of same 12h heat treatment times, is tentatively gradually reduced into the temperature of phase and no impurity needs, respectively 900
DEG C, 850 DEG C and 800 DEG C, and undoped with when pure Li7La3Zr2O12It is tetragonal phase under material room temperature, as shown in Figure 4.
Claims (7)
1. a kind of Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material, it is characterised in that stoichiometry
Formula is Li7-y+xLa3-xAxZr2-yTayO12, wherein, A represents one kind in doped chemical Sr, Ba, meets 0 ＜ y ＜, 2,0 ＜ x ＜ y,
Undoped Li7La3Zr2O12Material is tetragonal phase, and mixing Ta by Zr makes its stable structure in cubic phase.
2. the Li of divalent alkaline-earth metal as described in claim 1 and tantalum codope7La3Zr2O12Solid electrolyte material, it is special
Sign is：The doping of Ta ranging from 0.4 ＜ y ＜ 0.8.
3. the Li of divalent alkaline-earth metal as described in claim 1 and tantalum codope7La3Zr2O12Solid electrolyte material, it is special
Sign is：While stable cubic phase, divalent alkaline-earth metal element is adulterated at La, reaches the mesh for adjusting lithium concentration
, meanwhile, phase temperature is reduced into, acceleration of sintering improves material density；Ion of the ionic radius of Sr and Ba much larger than La half
Diameter (1.16), therefore lattice can also be expanded by mixing Sr and Ba, so as to adjust lithium ion mobility channel sized.
4. the Li of the divalent alkaline-earth metal and tantalum codope as described in claim 1-37La3Zr2O12It is prepared by solid electrolyte material
Method, it is characterised in that：By Li source compound, lanthanum source compound, divalent alkaline-earth metal compound, zirconium source compound and tantalum source
It is 7-y+x that object, which is closed, according to each element molar ratio:3-x:x:2-y:The ratio of y is uniformly mixed, by heat treatment early period tentatively into phase,
Tabletting is sintered again, obtains the solid electrolyte material, wherein, 0 ＜ y ＜, 2,0 ＜ x ＜ y, in order to make up lithium in sintering process
The volatilization in source, lithium source excessive 5%~20% during raw material proportioning.
5. the Li of divalent alkaline-earth metal as claimed in claim 4 and tantalum codope7La3Zr2O12Preparation method, it is characterised in that：
Lithium source excessive 10% during the raw material proportioning, raw material hybrid mode are ball milling.
6. the Li of the divalent alkaline-earth metal as claimed in claim 4 and tantalum codope7La3Zr2O12Solid electrolyte material
Preparation method, it is characterised in that：The heat treatment condition is 600 DEG C~950 DEG C 6~15h of processing.
7. the Li of the divalent alkaline-earth metal as claimed in claim 4 and tantalum codope7La3Zr2O12Solid electrolyte material
Preparation method, it is characterised in that：Tabletting sintering condition is that 3~15h is sintered at 1000 DEG C~1300 DEG C.
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| CN113402271B (en) * | 2021-06-04 | 2022-04-29 | 哈尔滨工业大学 | Method for improving density and conductivity of tantalum-doped garnet-type solid electrolyte |
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