CN103496740B - Electric field activated sintering method of solid electrolyte material - Google Patents
Electric field activated sintering method of solid electrolyte material Download PDFInfo
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- CN103496740B CN103496740B CN201310429512.5A CN201310429512A CN103496740B CN 103496740 B CN103496740 B CN 103496740B CN 201310429512 A CN201310429512 A CN 201310429512A CN 103496740 B CN103496740 B CN 103496740B
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Abstract
The invention provides an electric field activated sintering method of a solid electrolyte material Li7La3Zr2O12 (LLZO). The electric field activated sintering method comprises the following specific steps: ball-milling with a ball and mixing Li2O, La2O3 and ZrO2 powder, the mass percents of which are respectively 9.2-15.5%, 56.2-60.4% and 28.3-30.4%, wherein a zirconium oxide ball is used as a ball-milling medium, isopropanol is used as a solvent, and the ball-milling time is 12-36 hours; carrying out vacuum drying on ball-milling milled powder for 6-12 hours at the temperature of 80 DEG C; and carrying out electric field activated sintering, wherein the temperature is in the range from 800 to 1230 DEG C, the pressure is 0-100 MpaMPa, and a sintered sample has the room-temperature lithium-ion conductivity greater than 6*10<-4S>S/cm. Compared with a conventional solid-phase synthesis method, the electric field activated sintering method has the advantages that the synthesis reaction and the sintering compact process are completed in one step, the synthetic efficiency is improved to a large extent, the preparation technology is simplified, and the LLZO with the high lithium-ion conductivity is obtained.
Description
Technical field:
The invention belongs to solid electrolyte material preparing technical field, relate to a kind of solid electrolyte material Li particularly
7la
3zr
2o
12field activated sintering method.
Background technology:
Along with developing rapidly of mobile phone, computer etc., in the past few decades, lithium ion battery causes people and pays close attention to greatly.Current scientist is just attempting using these batteries to go to drive power vehicle, to avoid by the carbon dioxide of traditional gasoline-powered vehicles generation and other pollutants.It is high that these new application require that lithium ion battery has fail safe, and energy density is high, and the life-span is long and high temperature resistant.The current lithium ion battery based on liquid electrolyte can not meet these requirements, because the liquid organic electrolyte that they use is inflammable, volatile, easy leakage and high temperature time can decompose (C.A.Geiger, E.Alekseev, W.Weppner, Inorg.Chem..2011,50,1089-1097).Charging (secondary) all-solid lithium battery is considered to high-performance power source of future generation, and it is for commercial employing aprotic solvent, gel, or polymer electrolyte lithium-ion battery, in the miniaturization of battery, the stability under high temperature, energy density is high, the aspects such as the fail safe of battery have significant advantage (H.Xie, Y.Li, J.B.Goodenough, Materials Research Bulletin.2012,47,1229-1232).In all-solid-state battery, solid electrolyte also serves the effect of barrier film, simplifies the structure of battery.
At present, research and develop the solid lithium-ion electrolyte with Practical significance, require that it can have good stability (to carbon dioxide and moisture stabilization) in the environment simultaneously, in order to enable the all-solid-state battery of composition use lithium metal to have high energy density as negative pole, also wish that solid electrolytic mass-energy is stablized lithium metal and has higher decomposition voltage.A kind of high-lithium ion conductance of German Weppner seminar reported first in 2007 and low electronic conductance and there is good electrical chemical stability, the lithium ion conductor Li of the garnet structure of thermal stability
7la
3zr
2o
12, from the lithium ion solid electrolyte having report at present, Li
7la
3zr
2o
12(LLZO) in this field due to its high ionic conductivity, paid close attention to (R.Murugan, V.Thangadurai widely with the excellent compatibility of lithium metal and aerial stability, W.Weppner, Angew.Chem..2007,119,7925-7928).LLZO garnet type materials, it has two stable phases: Tetragonal and Emission in Cubic.Can Tetragonal be obtained under lower synthesis temperature compared with Emission in Cubic, but the volume conduction rate (~ 10 of Emission in Cubic
-3s/cm) than Tetragonal (~ 10
-6s/cm) much higher.In addition, Emission in Cubic LLZO is highly stable in atmosphere, and Tetragonal in atmosphere temperature be 100 ~ 150 DEG C and can undergo phase transition (J.Tan, A.Tiwari, Electrochemical and Solid-State Letters.2012,15 (3) A37-A39).Therefore, we more expect to obtain Emission in Cubic LLZO.
In research in early days, general employing conventional solid sintering process prepares solid electrolyte LLZO, grinding and the high-temperature heat treatment of material powder is comprised repeatedly in preparation process, Li element is an element easily lost, therefore the high temperature sintering duration is long, and material may be caused to occur, and obvious Li loses, and the more important thing is that this preparation method's energy consumption is large, sintering temperature is up to more than 1200 DEG C, and sintering time reaches more than 35 hours.Be necessary that developing a kind of low temperature method comprises less high-temperature step to obtain stoichiometric material.Kokal etc. have done some effort (I.Kokal, M.Somer, P.H.L.Notten, H.T.Hintzen, Solid State Ionics.2011,185,42-46) in this respect, and they use sol-gel process to synthesize LLZO.Although they have adopted the method to prepare LLZO, the thing of material is mainly Tetragonal mutually and has low-down ionic conductivity 3.12 × 10
-7s/cm.At present, the domestic preparation method about LLZO delivered is mostly conventional solid sintering process.CN102617140 discloses a kind of Li of class garnet structure of Sb doped
7-xla
3zr
2-xsb
xthe conventional solid reaction method of crystalline solid electrolyte, its sintering temperature is 1020 DEG C ~ 1230 DEG C, and sintering time reaches 18 ~ 24 hours.CN102867986 also announces a kind of B
3+, A1
3+, Ti
4+, Y
3+four component cation codope solid electrolyte Li
7la
3zr
2o
12conventional solid sintering process, this preparation process comprises repeatedly ball milling and process of lapping, and (700 ~ 900 DEG C are incubated 5 ~ 10 hours to need repeatedly substep heat treatment and long-time heat preservation, 1150 ~ 1250 DEG C are incubated 10 ~ 30 hours, and 1200 ~ 1300 DEG C are incubated 10 ~ 20 hours) just can make lithium ion solid electrolyte.These illustrate that the method preparing LLZO of now having invented exists the problems such as preparation process is loaded down with trivial details, sintering temperature is high, sintering time is long, and therefore we expect to find a kind of preparation method efficiently to obtain high performance LLZO solid electrolyte material.
Summary of the invention:
Technical problem to be solved by this invention is: the problems such as the long and low lithium ion conductivity of high, the sintering time of sintering temperature existed for current technology of preparing, provide a kind of solid electrolyte material Li
7la
3zr
2o
12sintering method, then the method carries out field activated sintering by ball mill mixing, be intended to obtain high-compactness, high-lithium ion conductance Emission in Cubic LLZO, and reduce sintering temperature and simplify preparation technology.
The present invention solves its technical problem and adopts following technical scheme:
The field activated sintering method of solid electrolyte material provided by the invention is that one utilizes field activated sintering method to prepare solid electrolyte material Li
7la
3zr
2o
12, the method comprises the following steps:
(1) pretreatment of raw material: use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder,
And to lanthana at 900 DEG C of constant temperature calcinings;
(2) raw material weighing, mixing: be 9.2 ~ 15.5%, 56.2 ~ 60.4% and 28.3 ~ 30.4% weigh Li respectively according to mass fraction
2o, La
2o
3and ZrO
2powder, then puts it in ball grinder and carries out ball milling, and is ball-milling medium with zirconia ball, take isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1 ~ 3:1, and the powder after ball milling puts into vacuum drying chamber, drying 6 ~ 12 hours under 80 DEG C of conditions;
(3) field activated sintering: insert in graphite jig by dried powder, then sinters under inert gas shielding, and the crystalline ceramics solid electrolyte material after sintering is described solid electrolyte material.
Described Li
2o powder can by LiOH powder or Li
2cO
3powder is replaced.
Described ball grinder can be the ball grinder of zirconia material, is 100 ~ 300 revs/min of lower ball millings 12 ~ 36 hours at rotational speed of ball-mill.
The particle diameter of the powder after described ball milling can be 1 ~ 5 μm.
Described inert gas can be argon gas or nitrogen.
Described field activated sintering technique can be:
(1) keep pressure to be 0MPa when temperature < 800 DEG C, and be incubated 1 ~ 5 minute, complete the synthesis of LLZO;
(2) sintering pressure is pressurized to rapidly subsequently until sintering terminates, be specially: sintering pressure be 1 ~ 100MPa, heating rate is 30 ~ 300 DEG C/min, sintering temperature to be 800 ~ 1230 DEG C and temperature retention time be under 1 ~ 20 minute sintering, products obtained therefrom is solid electrolyte material of the present invention.
Solid electrolyte material prepared by the present invention, its technical parameter can be: in temperature range 800 ~ 1230 DEG C, the thing of gained sample is Emission in Cubic mutually, lithium ion conductivity>=6 × 10 under room temperature
-4s/cm, density>=99%.
The present invention compared with prior art has following main advantage:
One, adopt field activated sintering to prepare sample, the sample density of sintering is high, and crystallite dimension is little, homogeneous, and lithium ion conductivity is high.After sintering, sample can obtain and be greater than 6 × 10
-4the room temperature lithium ion conductivity of S/cm, and sample density is higher than 99%.
Its two, the extremely short loss reducing Li of sintering time of field activated sintering, the sintering temperature (800 DEG C) obtaining Emission in Cubic have dropped 430 DEG C compared with conventional solid-state method (1230 DEG C).
Its three, the material powder of field activated sintering is obtained by a ball mill mixing, and preparation technology is simple.Compared with conventional solid synthetic method, synthetic reaction and densified sintering product process one step complete by preparation method of the present invention, improve combined coefficient to a great extent.
Its four, relative to the LLZO sintering temperature that Weppner etc. reports, sintering temperature of the present invention is lower, for production in enormous quantities, can energy efficient, can effectively reduce costs.
Accompanying drawing illustrates:
Fig. 1 is Li of the present invention
7la
3zr
2o
12the X-ray diffractogram that system sinters in different temperatures.
Fig. 2 is the sample Li that the present invention sinters at 1100 DEG C
7la
3zr
2o
12aC impedance curve under room temperature.
Fig. 3 is the sample Li that the present invention sinters at 1150 DEG C
7la
3zr
2o
12aC impedance curve under room temperature.
Fig. 4 is Li
7la
3zr
2o
12solid electrolyte micro-structure diagram.
Embodiment:
Be further elaborated the present invention below in conjunction with embodiment and accompanying drawing, the present invention is not limited to following example.
Embodiment 1:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 9.2%, 60.4% and 30.4% weigh synthesis 5g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 0.46g, lanthana (La
2o
3, 99.99%) and 3.02g, zirconia (ZrO
2, 99.9%) and 1.52g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 3:1, the lower ball milling of rotational speed of ball-mill 100 revs/min 36 hours.Powder after ball milling puts into vacuum drying chamber, drying 6 hours under 80 DEG C of conditions.Taking dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 5 minutes when temperature < 800 DEG C; Be pressurized to 100MPa rapidly subsequently until sintering terminates, under argon shield, sintering temperature is 800 DEG C, and temperature retention time is 1 minute, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 2:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 10.1%, 59.8% and 30.1% weigh synthesis 5g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 0.505g, lanthana (La
2o
3, 99.99%) and 2.99g, zirconia (ZrO
2, 99.9%) and 1.505g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 3:1, the lower ball milling of rotational speed of ball-mill 200 revs/min 24 hours.Powder after ball milling puts into vacuum drying chamber, drying 6 hours under 80 DEG C of conditions.Taking dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 4 minutes when temperature < 800 DEG C; Be pressurized to 80MPa rapidly subsequently until sintering terminates, under argon shield, sintering temperature is 900 DEG C, and temperature retention time is 4 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 3:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 11.8%, 58.7% and 29.5% weigh synthesis 10g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 1.18g, lanthana (La
2o
3, 99.99%) and 5.87g, zirconia (ZrO
2, 99.9%) and 2.95g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1, the lower ball milling of rotational speed of ball-mill 300 revs/min 12 hours.Powder after ball milling puts into vacuum drying chamber, drying 8 hours under 80 DEG C of conditions.Taking dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 3 minutes when temperature < 800 DEG C; Be pressurized to 60MPa rapidly subsequently until sintering terminates, under argon shield, sintering temperature is 1000 DEG C, and temperature retention time is 8 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 4:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 12.4%, 58.2% and 29.4% weigh synthesis 10g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 1.24g, lanthana (La
2o
3, 99.99%) and 5.82g, zirconia (ZrO
2, 99.9%) and 2.94g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1, the lower ball milling of rotational speed of ball-mill 300 revs/min 12 hours.Powder after ball milling puts into vacuum drying chamber, drying 10 hours under 80 DEG C of conditions.Taking dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 2 minutes when temperature < 800 DEG C; Be pressurized to 40MPa rapidly subsequently until sintering terminates, under nitrogen protection, sintering temperature is 1100 DEG C, and temperature retention time is 12 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 5:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 14.0%, 57.2% and 28.8% weigh synthesis 10g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 1.40g, lanthana (La
2o
3, 99.99%) and 5.72g, zirconia (ZrO
2, 99.9%) and 2.88g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1, the lower ball milling of rotational speed of ball-mill 300 revs/min 12 hours.Powder after ball milling puts into vacuum drying chamber, drying 8 hours under 80 DEG C of conditions.Getting dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 1 minute when temperature < 800 DEG C; Be pressurized to 20MPa rapidly subsequently until sintering terminates, under nitrogen protection, sintering temperature is 1150 DEG C, and temperature retention time is 16 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 6:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 15.5%, 56.2% and 28.3% weigh synthesis 10g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 1.55g, lanthana (La
2o
3, 99.99%) and 5.62g, zirconia (ZrO
2, 99.9%) and 2.83g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1, the lower ball milling of rotational speed of ball-mill 300 revs/min 12 hours.Powder after ball milling puts into vacuum drying chamber, drying 10 hours under 80 DEG C of conditions.Getting dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 2 minutes when temperature < 800 DEG C; Be pressurized to 10MPa rapidly subsequently until sintering terminates, under nitrogen protection, sintering temperature is 1200 DEG C, and temperature retention time is 20 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 7:
Use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana (La
2o
3) at 900 DEG C of constant temperature calcinings.Be 12.4%, 58.2% and 29.4% weigh synthesis 10g needed raw material powder lithia (Li respectively according to mass fraction
2o, 99.9%) 1.24g, lanthana (La
2o
3, 99.99%) and 5.82g, zirconia (ZrO
2, 99.9%) and 2.94g.The ball grinder that above-mentioned three kinds of powder put into zirconia material being carried out ball milling, and is ball-milling medium with zirconia ball, took isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1, the lower ball milling of rotational speed of ball-mill 300 revs/min 12 hours.Powder after ball milling puts into vacuum drying chamber, drying 8 hours under 80 DEG C of conditions.Getting dried powder 1.5g inserts in graphite jig, keeps pressure to be 0MPa, and be incubated 3 minutes when temperature < 800 DEG C; Be pressurized to 1MPa rapidly subsequently until sintering terminates, under nitrogen protection, sintering temperature is 1230 DEG C, and temperature retention time is 4 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
To the Li prepared
7la
3zr
2o
12sample carries out X-ray diffraction analysis, to determine that its thing is formed and crystal structure mutually, obtains Fig. 1.With reference to Fig. 1, from Li
7la
3zr
2o
12the XRD characteristic diffraction peak of sample can be found out, after oversintering, the compound obtained in 800 ~ 1230 DEG C of temperature ranges is Emission in Cubic class garnet structure.
Measure the Li prepared
7la
3zr
2o
12the AC impedance curve of system sample, obtains Fig. 2 and Fig. 3, as shown in Figure 3 its 1150 DEG C sintering sample room temperature under lithium ion conductivity up to 6.01 × 10
-4s/cm.
To gained Emission in Cubic Li
7la
3zr
2o
12sample carries out sem test, obtains its microstructure Fig. 4.After sintering, solid electrolyte microstructure is fine and close as can be seen from Figure 4, and without hole, crystal boundary combines closely, and major part is transgranular fracture.
In above-described embodiment 1-7, the Li adopted
2o powder can by LiOH powder or Li
2cO
3powder is replaced.
Solid electrolyte material prepared by above-described embodiment, its technical parameter can be: in temperature range 800 ~ 1230 DEG C, the thing of gained sample is Emission in Cubic mutually, lithium ion conductivity>=6 × 10 under room temperature
-4s/cm, density>=99%.
Claims (6)
1. a field activated sintering method for solid electrolyte material, is characterized in that one utilizes field activated sintering method to prepare solid electrolyte material Li
7la
3zr
2o
12, the method comprises the following steps:
(1) pretreatment of raw material: use lithia Li
2o, lanthana La
2o
3, zirconia ZrO
2powder as material powder, and to lanthana at 900 DEG C of constant temperature calcinings;
(2) raw material weighing, mixing: be 9.2 ~ 15.5%, 56.2 ~ 60.4% and 28.3 ~ 30.4% weigh Li respectively according to mass fraction
2o, La
2o
3and ZrO
2powder, then puts it in ball grinder and carries out ball milling, and is ball-milling medium with zirconia ball, take isopropyl alcohol as solvent, and isopropyl alcohol and powder quality are than being 6:1 ~ 3:1, and the powder after ball milling puts into vacuum drying chamber, drying 6 ~ 12 hours under 80 DEG C of conditions;
(3) field activated sintering: insert in graphite jig by dried powder, then sinters under inert gas shielding, and the crystalline ceramics solid electrolyte material after sintering is described solid electrolyte material;
Described field activated sintering technique is: keep pressure to be 0MPa when temperature < 800 DEG C, and be incubated 1 ~ 5 minute; Be pressurized to sintering pressure rapidly subsequently until sintering terminates, sintering pressure is 1 ~ 100MPa, heating rate is 30 ~ 300 DEG C/min, sintering temperature be 800 ~ 1230 DEG C and temperature retention time is 1 ~ 20 minute, obtain described solid electrolyte material.
2. field activated sintering method according to claim 1, is characterized in that described Li
2o powder is by LiOH powder or Li
2cO
3powder is replaced.
3. field activated sintering method according to claim 1, is characterized in that described ball grinder is the ball grinder of zirconia material, is 100 ~ 300 revs/min of lower ball millings 12 ~ 36 hours at rotational speed of ball-mill.
4. field activated sintering method according to claim 1, is characterized in that the particle diameter of the powder after described ball milling is 1 ~ 5 μm.
5. field activated sintering method according to claim 1, is characterized in that described inert gas is argon gas or nitrogen.
6. the field activated sintering method according to claim arbitrary in claim 1-5, it is characterized in that obtained solid electrolyte material, its technical parameter is: in temperature range 800 ~ 1230 DEG C, the thing of gained sample is Emission in Cubic mutually, lithium ion conductivity>=6 × 10 under room temperature
-4s/cm, density>=99%.
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| CN104124467B (en) * | 2014-07-22 | 2016-06-01 | 武汉理工大学 | A kind of method utilizing lithium lanthanum zirconium oxygen presoma coated powder to prepare solid electrolyte |
| CN108946807A (en) * | 2017-05-18 | 2018-12-07 | 珠海市赛纬电子材料股份有限公司 | A kind of solid electrolyte Li7La3Zr2O12Raw powder's production technology |
| US20200058956A1 (en) * | 2017-08-18 | 2020-02-20 | Robert Bosch Gmbh | Composite Reinforced Solid Electrolyte to Prevent Protrusions |
| CN111477949B (en) * | 2017-08-30 | 2021-11-23 | 清陶（昆山）能源发展有限公司 | Lithium ion solid electrolyte with superstructure |
| CN108695551A (en) * | 2018-04-08 | 2018-10-23 | 湖北工业大学 | A kind of molten-salt growth method preparation garnet-type solid electrolyte Li7La3Zr2O12The method of block |
| CN108793987B (en) * | 2018-06-29 | 2020-07-10 | 华中科技大学 | Lithium ion conductive oxide solid electrolyte and preparation method thereof |
| CN109361014B (en) * | 2018-09-12 | 2020-07-10 | 北京理工大学 | Solid electrolyte composite material of lithium secondary battery, preparation method and lithium secondary battery |
| CN109608192A (en) * | 2018-12-29 | 2019-04-12 | 中原工学院 | A kind of method that electric field-assisted method prepares LLZO series battery material |
| CN110994010A (en) * | 2019-12-31 | 2020-04-10 | 中兴高能技术有限责任公司 | Halide solid electrolyte, preparation method thereof and lithium ion battery |
| CN113429199A (en) * | 2021-07-20 | 2021-09-24 | 西南交通大学 | Sintering method of compact solid electrolyte LATP |
| CN116655380A (en) * | 2023-05-26 | 2023-08-29 | 香河昆仑新能源材料股份有限公司 | Garnet type solid electrolyte and preparation method and application thereof |
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| Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12;Ramaswamy Murugan et al.;《Angew. Chem. Int. Ed.》;20070905;第46卷;7778-7781 * |
| 锂含量与烧结时间对固体电解质Li7La3Zr2O12电导率的影响;黄冕 等;《硅酸盐学报》;20130831;第41卷(第8期);1042-1045 * |
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