CN103496740A - Electric field activated sintering method of solid electrolyte material - Google Patents
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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 the solid electrolyte material preparing technical field, relate to particularly a kind of solid electrolyte material Li
7la
3zr
2o
12electric field activated sintering method.
Background technology:
Along with developing rapidly of mobile phone, computer etc., in the past few decades in lithium ion battery caused that people pay close attention to greatly.Scientist is just attempting using these batteries to remove to drive power vehicle at present, with carbonic acid gas and other pollutents of avoiding being produced by traditional gasoline-powered vehicles.These new application requiring lithium ion batteries have 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, can decompose (C.A.Geiger, E.Alekseev, W.Weppner when easy leakage and high temperature, Inorg.Chem..2011,50,1089-1097).Charging (secondary) all-solid lithium battery is considered to high-performance propulsion source of future generation, and it is for the non-proton solution of commercial employing, 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 security 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 has also played the effect of barrier film, has simplified the structure of battery.
At present, research and develop the solid lithium-ion electrolyte with Practical significance, require it can in environment, there is satisfactory stability (to carbonic acid gas and moisture stabilization) simultaneously, for the all-solid-state battery that makes to form can be used metallic lithium to have high energy density as negative pole, also wish that solid electrolytic mass-energy stablizes metallic lithium and have a higher decomposition voltage.German Weppner seminar reported first in 2007 a kind of high-lithium ion electricity lead and hang down electronic conductance and there is the good electrical chemical stability, the lithium ion conductor Li of the garnet structure of thermostability
7la
3zr
2o
12, from having at present the lithium ion solid electrolyte of report, Li
7la
3zr
2o
12(LLZO) in this field due to its high ionic conductivity, paid close attention to widely (R.Murugan, V.Thangadurai with excellent compatibility and the aerial stability of lithium metal, W.Weppner, Angew.Chem..2007,119,7925-7928).LLZO carbuncle type material, it has two stable phases: Tetragonal and Emission in Cubic.Compare under lower synthesis temperature and can obtain Tetragonal 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 air, and Tetragonal temperature in air is 100～150 ℃, 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, the traditional solid sintering technology of general employing prepares solid electrolyte LLZO, the grinding and the high-temperature heat treatment that comprise repeatedly material powder in preparation process, the Li element is an easily element of loss, so the high temperature sintering time length is long, may cause material obvious Li loss to occur, the more important thing is that this preparation method's energy consumption is large, sintering temperature is up to more than 1200 ℃, and sintering time reached more than 35 hours.Be necessary to develop a kind of low temperature method and comprise less high-temperature step in order to obtain stoichiometric material.In this respect Kokal etc. done some effort (I.Kokal, M.Somer, P.H.L.Notten, H.T.Hintzen, Solid State Ionics.2011,185,42-46), they use sol-gel method to synthesize LLZO.Although they adopt the method to prepare LLZO, the phase of material is mainly Tetragonal and has low-down ionic conductivity 3.12 * 10
-7s/cm.At present, the domestic preparation method about LLZO who has delivered is mostly traditional solid sintering technology.CN102617140 has announced a kind of Li of class garnet structure of antimony doping
7-xla
3zr
2-xsb
xtraditional solid reaction process of crystalline state solid electrolyte material, its sintering temperature is 1020 ℃～1230 ℃, sintering time reaches 18～24 hours.CN102867986 also announces a kind of B
3+, A1
3+, Ti
4+, Y
3+four component positively charged ion codoped solid electrolyte Li
7la
3zr
2o
12traditional solid sintering technology, this preparation process comprises repeatedly ball milling and process of lapping, and need repeatedly substep thermal treatment and long-time insulation (700～900 ℃ of insulations 5～10 hours, 1150～1250 ℃ are incubated 10～30 hours, and 1200～1300 ℃ are incubated 10～20 hours) just can make lithium ion solid electrolyte.There are the problems such as preparation process is loaded down with trivial details, sintering temperature is high, sintering time is long in these explanation methods that prepare LLZO of now having invented, so we expect to find a kind of efficient preparation method and obtain high performance LLZO solid electrolyte material.
Summary of the invention:
Technical problem to be solved by this invention is: the sintering temperature existed for current technology of preparing is high, sintering time long and the problem such as low lithium ion conductivity, and a kind of solid electrolyte material Li is provided
7la
3zr
2o
12sintering method, then the method carries out electric field activated sintering by ball mill mixing, is intended to obtain the Emission in Cubic LLZO that high-compactness, high-lithium ion electricity are led, and reduces sintering temperature and simplify preparation technology.
The present invention solves its technical problem and adopts following technical scheme:
The electric field activated sintering method of solid electrolyte material provided by the invention is that a kind of electric field activated sintering method of utilizing prepares solid electrolyte material Li
7la
3zr
2o
12, the method comprises the following steps:
(1) raw materials pretreatment: use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder,
And to lanthanum trioxide at 900 ℃ of constant temperature calcinings;
(2) raw material weighing, mixing: according to massfraction, be 9.2～15.5%, 56.2～60.4% and 28.3～30.4% difference weighing Li
2o, La
2o
3and ZrO
2powder, then put it in ball grinder and carry out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1～3:1, and the powder after ball milling is put into vacuum drying oven, under 80 ℃ of conditions dry 6～12 hours;
(3) electric field activated sintering: dried powder is inserted in graphite jig, then under protection of inert gas, carry out sintering, the crystalline ceramics solid electrolyte material after sintering is described solid electrolyte material.
Described Li
2the O powder can be by LiOH powder or Li
2cO
3powder is replaced.
Described ball grinder can be the ball grinder of zirconium white material, at rotational speed of ball-mill, is 100～300 rev/mins of lower ball millings 12～36 hours.
The particle diameter of the powder after described ball milling can be 1～5 μ m.
Described rare gas element can be argon gas or nitrogen.
Described electric field activated sintering technique can be:
(1) keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 1～5 minute, completes the synthetic of LLZO;
(2) be pressurized to sintering pressure rapidly subsequently until sintering finishes, be specially: at sintering pressure, be that 1～100MPa, temperature rise rate are that 30～300 ℃/minute, sintering temperature are that 800～1230 ℃ and soaking time are 1～20 minute lower sintering, products obtained therefrom is solid electrolyte material of the present invention.
The solid electrolyte material that the present invention is prepared, its technical parameter can be: in 800～1230 ℃ of temperature ranges, the phase of gained sample is Emission in Cubic, lithium ion conductivity under room temperature>=6 * 10
-4s/cm, density>=99%.
The present invention compared with prior art has advantages of following main:
One, adopt electric field activated sintering to prepare sample, and the sample density of sintering is high, and grain-size 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 the sample density is higher than 99%.
Its two, the extremely short loss that reduces Li of the sintering time of electric field activated sintering, the sintering temperature (800 ℃) that obtains Emission in Cubic is compared and has been descended 430 ℃ with conventional solid-state method (1230 ℃).
Its three, the material powder of electric field activated sintering obtains by a ball mill mixing, preparation technology is simple.With traditional solid-phase synthesis, compare, preparation method of the present invention completes building-up reactions and densified sintering product process one step, has improved to a great extent combined coefficient.
Its four, with respect to the LLZO sintering temperature of the report such as Weppner, sintering temperature of the present invention is lower, for production in enormous quantities, can energy efficient, can effectively reduce costs.
The accompanying drawing explanation:
Fig. 1 is Li of the present invention
7la
3zr
2o
12system is at the X-ray diffractogram of differing temps sintering.
Fig. 2 is the sample Li of the present invention at 1100 ℃ of lower sintering
7la
3zr
2o
12alternating-current impedance curve under room temperature.
Fig. 3 is the sample Li of the present invention at 1150 ℃ of lower sintering
7la
3zr
2o
12alternating-current impedance curve under room temperature.
Fig. 4 is Li
7la
3zr
2o
12the solid electrolyte micro-structure diagram.
Embodiment:
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated, the present invention is not limited to following example.
Embodiment 1:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 5g desired raw material powder Lithium Oxide 98min (Li of 9.2%, 60.4% and 30.4% difference weighing
2o, 99.9%) 0.46g, lanthanum trioxide (La
2o
3, 99.99%) and 3.02g, zirconium white (ZrO
2, 99.9%) and 1.52g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 3:1,100 rev/mins of lower ball millings of rotational speed of ball-mill 36 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 6 hours.Take dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 5 minutes; Be pressurized to 100MPa rapidly subsequently until sintering finishes, under argon shield, sintering temperature is 800 ℃, and soaking time is 1 minute, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 2:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 5g desired raw material powder Lithium Oxide 98min (Li of 10.1%, 59.8% and 30.1% difference weighing
2o, 99.9%) 0.505g, lanthanum trioxide (La
2o
3, 99.99%) and 2.99g, zirconium white (ZrO
2, 99.9%) and 1.505g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 3:1,200 rev/mins of lower ball millings of rotational speed of ball-mill 24 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 6 hours.Take dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 4 minutes; Be pressurized to 80MPa rapidly subsequently until sintering finishes, under argon shield, sintering temperature is 900 ℃, and soaking time is 4 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 3:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 10g desired raw material powder Lithium Oxide 98min (Li of 11.8%, 58.7% and 29.5% difference weighing
2o, 99.9%) 1.18g, lanthanum trioxide (La
2o
3, 99.99%) and 5.87g, zirconium white (ZrO
2, 99.9%) and 2.95g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1,300 rev/mins of lower ball millings of rotational speed of ball-mill 12 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 8 hours.Take dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 3 minutes; Be pressurized to 60MPa rapidly subsequently until sintering finishes, under argon shield, sintering temperature is 1000 ℃, and soaking time is 8 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 4:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 10g desired raw material powder Lithium Oxide 98min (Li of 12.4%, 58.2% and 29.4% difference weighing
2o, 99.9%) 1.24g, lanthanum trioxide (La
2o
3, 99.99%) and 5.82g, zirconium white (ZrO
2, 99.9%) and 2.94g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1,300 rev/mins of lower ball millings of rotational speed of ball-mill 12 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 10 hours.Take dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 2 minutes; Be pressurized to 40MPa rapidly subsequently until sintering finishes, under nitrogen protection, sintering temperature is 1100 ℃, and soaking time is 12 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 5:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 10g desired raw material powder Lithium Oxide 98min (Li of 14.0%, 57.2% and 28.8% difference weighing
2o, 99.9%) 1.40g, lanthanum trioxide (La
2o
3, 99.99%) and 5.72g, zirconium white (ZrO
2, 99.9%) and 2.88g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1,300 rev/mins of lower ball millings of rotational speed of ball-mill 12 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 8 hours.Get dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 1 minute; Be pressurized to 20MPa rapidly subsequently until sintering finishes, under nitrogen protection, sintering temperature is 1150 ℃, and soaking time is 16 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 6:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 10g desired raw material powder Lithium Oxide 98min (Li of 15.5%, 56.2% and 28.3% difference weighing
2o, 99.9%) 1.55g, lanthanum trioxide (La
2o
3, 99.99%) and 5.62g, zirconium white (ZrO
2, 99.9%) and 2.83g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1,300 rev/mins of lower ball millings of rotational speed of ball-mill 12 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 10 hours.Get dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 2 minutes; Be pressurized to 10MPa rapidly subsequently until sintering finishes, under nitrogen protection, sintering temperature is 1200 ℃, and soaking time is 20 minutes, and products obtained therefrom is solid electrolyte material of the present invention.
Embodiment 7:
Use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide (La
2o
3) at 900 ℃ of constant temperature calcinings.According to massfraction, be the synthetic 10g desired raw material powder Lithium Oxide 98min (Li of 12.4%, 58.2% and 29.4% difference weighing
2o, 99.9%) 1.24g, lanthanum trioxide (La
2o
3, 99.99%) and 5.82g, zirconium white (ZrO
2, 99.9%) and 2.94g.The ball grinder that above-mentioned three kinds of powder are put into to the zirconium white material carried out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1,300 rev/mins of lower ball millings of rotational speed of ball-mill 12 hours.Powder after ball milling is put into vacuum drying oven, and under 80 ℃ of conditions, drying is 8 hours.Get dried powder 1.5g and insert in graphite jig, keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 3 minutes; Be pressurized to 1MPa rapidly subsequently until sintering finishes, under nitrogen protection, sintering temperature is 1230 ℃, and soaking 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 its phase, forms and crystalline structure, obtains Fig. 1.With reference to Fig. 1, from Li
7la
3zr
2o
12the XRD characteristic diffraction peak of sample can find out, after oversintering, the compound obtained in 800～1230 ℃ of temperature ranges is Emission in Cubic class garnet structure.
The Li that mensuration prepares
7la
3zr
2o
12the alternating-current impedance curve of system sample, obtain Fig. 2 and Fig. 3, as shown in Figure 3 under its room temperature of sample at 1150 ℃ of sintering 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.Solid electrolyte microstructure densification after sintering as can be seen from Figure 4, without hole, crystal boundary is in conjunction with tight, and major part is transgranular fracture.
In above-described embodiment 1-7, the Li adopted
2the O powder can be by LiOH powder or Li
2cO
3powder is replaced.
The solid electrolyte material that above-described embodiment is prepared, its technical parameter can be: in 800～1230 ℃ of temperature ranges, the phase of gained sample is Emission in Cubic, lithium ion conductivity under room temperature>=6 * 10
-4s/cm, density>=99%.
Claims (8)
1. the electric field activated sintering method of a solid electrolyte material, is characterized in that a kind of electric field activated sintering method of utilizing prepares solid electrolyte material Li
7la
3zr
2o
12, the method comprises the following steps:
(1) raw materials pretreatment: use Lithium Oxide 98min Li
2o, lanthanum trioxide La
2o
3, zirconium white ZrO
2powder is as material powder, and to lanthanum trioxide at 900 ℃ of constant temperature calcinings;
(2) raw material weighing, mixing: according to massfraction, be 9.2～15.5%, 56.2～60.4% and 28.3～30.4% difference weighing Li
2o, La
2o
3and ZrO
2powder, then put it in ball grinder and carry out ball milling, and take zirconia ball as ball-milling medium, take Virahol as solvent, and Virahol and powder quality be than being 6:1～3:1, and the powder after ball milling is put into vacuum drying oven, under 80 ℃ of conditions dry 6～12 hours;
(3) electric field activated sintering: dried powder is inserted in graphite jig, then under protection of inert gas, carry out sintering, the crystalline ceramics solid electrolyte material after sintering is described solid electrolyte material.
2. electric field activated sintering method according to claim 1, is characterized in that described Li
2the O powder is by LiOH powder or Li
2cO
3powder is replaced.
3. electric field activated sintering method according to claim 1, is characterized in that the ball grinder that described ball grinder is the zirconium white material, at rotational speed of ball-mill, is 100～300 rev/mins of lower ball millings 12～36 hours.
4. electric 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 μ m.
5. electric field activated sintering method according to claim 1, is characterized in that described rare gas element is argon gas or nitrogen.
6. electric field activated sintering method according to claim 1 is characterized in that described electric field activated sintering technique is:
(1) keeping pressure during in temperature<800 ℃ is 0MPa, and is incubated 1～5 minute, completes the synthetic of LLZO;
(2) be pressurized to sintering pressure rapidly subsequently until sintering finishes, obtain described solid electrolyte material.
7. electric field activated sintering method according to claim 6, is characterized in that in step (2), at sintering pressure, is that 1～100MPa, temperature rise rate are that 30～300 ℃/minute, sintering temperature are that 800～1230 ℃ and soaking time are 1～20 minute lower sintering.
8. according to the described electric field activated sintering of arbitrary claim method in claim 1-7, it is characterized in that obtained solid electrolyte material, its technical parameter is: in 800～1230 ℃ of temperature ranges, the phase of gained sample is Emission in Cubic, lithium ion conductivity under room temperature>=6 * 10
-4s/cm, density>=99%.
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| CN111477949A (en) * | 2017-08-30 | 2020-07-31 | 清陶（昆山）能源发展有限公司 | Lithium ion solid electrolyte with superstructure |
| CN113429199A (en) * | 2021-07-20 | 2021-09-24 | 西南交通大学 | Sintering method of compact solid electrolyte LATP |
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| CN104124467A (en) * | 2014-07-22 | 2014-10-29 | 武汉理工大学 | Method for preparing solid electrolyte by using lithium lanthanum zirconium oxide precursor coated powder |
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| CN110945682A (en) * | 2017-08-18 | 2020-03-31 | 罗伯特·博世有限公司 | Composite reinforced solid electrolyte for preventing protrusion |
| CN111477949A (en) * | 2017-08-30 | 2020-07-31 | 清陶（昆山）能源发展有限公司 | Lithium ion solid electrolyte with superstructure |
| 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 |
| CN108793987A (en) * | 2018-06-29 | 2018-11-13 | 华中科技大学 | A kind of new type lithium ion conductive oxide solid electrolyte and preparation method thereof |
| CN108793987B (en) * | 2018-06-29 | 2020-07-10 | 华中科技大学 | Lithium ion conductive oxide solid electrolyte and preparation method thereof |
| CN109361014A (en) * | 2018-09-12 | 2019-02-19 | 北京理工大学 | A kind of lithium secondary battery solid state electrolysis composite material, preparation method and lithium secondary battery |
| 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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