CN110534681A - Conduct the tubular ceramic film and preparation method thereof of ion - Google Patents
Conduct the tubular ceramic film and preparation method thereof of ion Download PDFInfo
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- CN110534681A CN110534681A CN201810545465.3A CN201810545465A CN110534681A CN 110534681 A CN110534681 A CN 110534681A CN 201810545465 A CN201810545465 A CN 201810545465A CN 110534681 A CN110534681 A CN 110534681A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of tubular ceramic films for conducting ion, and preparing raw material includes solid electrolyte powder and adhesive, and wherein the mass percent of adhesive is 0~10%；The total ionic conductivity of tubular ceramic film room temperature is more than 1 × 10‑4S/cm, 100~150 DEG C of total ionic conductivities are 1 × 10‑2S/cm or more；The present invention also provides the preparation method of tubular ceramic film, including premix raw material, preformed blank, heat treatment, cooling polishing.Using solid electrolyte as ceramic film raw material, it is prepared into tubular ceramic film, different from stacked ceramic membrane in the prior art, the problem of overcoming the poor toughness of solid electrolyte block materials itself, and resulting tubular ceramic film maintains good ionic conductivity under room temperature or lower temperature, it can be suitable for more extensive battery shape and operational safety, guarantee high-energy density and the high circulation service life of battery.
Description
Technical field
The present invention relates to a kind of battery materials, more particularly, to a kind of ceramic membrane materials for conducting ion, while being related to it
Preparation method.
Background technique
It is in recent years increasingly reducing for the global non-renewable energy resources petroleum reserves of reply and continuing for global warming gas
It is soaring, natural resources and natural environment for the survival of mankind are protected, various countries will develop new energy and new-energy automobile one after another
Grand strategy as national development selects.New energy refers to the unconventional energy resource developed and used on the basis of new technology, including
Wind energy, solar energy, ocean energy, geothermal energy, biomass energy, Hydrogen Energy, nuclear energy etc..New forms of energy resource potentiality are big, can continuous utilization, In
Meet energy demand, improve energy resource structure, reduce environmental pollution etc. has played important function.Establish efficient energy storage and
Energy conversion device is providing crucial peak load shifting technical support, adjusts electric power, improves the utilization efficiency and electricity of power generation
Mechanical mass promotes extensive use of renewable energy etc. to be of great significance.On the other hand, power battery is answered extensively
In pure electric vehicle and hybrid power new-energy automobile, the dependence to non-renewable energy resources petroleum can be not only reduced, but also
It can be reduced carbon dioxide gas discharge, alleviate the pressure of environmental pollution.Current application is in consumable electronic product, power and storage
The commercialization rechargeable battery in energy field is based on liquid lithium ionic cell, lead-acid accumulator and sodium-sulphur battery.Wherein liquid lithium
Ion battery mainly uses the liquid electrolyte containing flammable organic solvent, and electrolyte and electrode material can occur side reaction, lead
The problems such as tankage irreversible decaying occurs, also brings along flatulence, leakage is sent a telegraph, its service life and safety are affected
Can, while the liquid lithium ionic cell of existing system is not able to satisfy it in power and energy storage field in energy density and power density
Large-scale application.And using inorganic solid electrolyte as the solid state lithium battery of diaphragm and conducting lithium ions, there is security performance
The advantages that height has extended cycle life, and operating temperature range is wide, and energy density is high, as energy storage device in new-energy automobile and intelligence
Electrical network field is with a wide range of applications.
Solid electrolyte ceramic membrane is both the solid electrolyte and isolation positive and negative anodes of diversion in energy storage device
Effect, is the critical component of battery.Current reported electrolytic tube is mainly the β "-Al for being applied to sodium-sulphur battery2O3Ceramics
Pipe, conductivity can reach 10 at 300 DEG C-2The S/cm order of magnitude.Using lithium ion inorganic solid electrolyte as the solid-state lithium electricity of diaphragm
The energy storage devices such as pond, lithium-sulfur cell, lithium sky battery, can be used lithium anode, theoretically also energy density with higher
And cycle life, generated side reaction when avoiding using liquid electrolyte, and can be improved safety.Due to inorganic solid-state
Electrolyte slug material shortage toughness, thus be applied in lithium battery mostly use it is stacked, it is in the form of a single to limit solid state electrolysis
The application of matter；Furthermore it as above analyzes existing with β "-Al2O3The ceramic sodium-sulphur battery for electrolyte ability in 300 DEG C or more of high temperature
With good conductivity, normal operating temperature is at 300~350 DEG C, and this running temperature greatly reduces battery security.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of tubular structure dielectric film based on ionic conduction, in room
Temperature or 150 DEG C or less are with preferable ionic conductivity (10-2The S/cm order of magnitude), stacked battery design theory can be got rid of
And it is applied in the batteries such as solid state lithium battery.
The technical solution of the present invention is to provide a kind of tubular ceramic films for conducting ion, and preparing raw material includes solid electrolyte
Powder and adhesive, wherein the mass percent of adhesive is 0~10%；The total ionic conductivity of tubular ceramic film room temperature is more than
1×10-4S/cm, 100~150 DEG C of total ionic conductivities are 1 × 10-2S/cm or more.
Further, tubular ceramic film is closed at one end, and length is 10~600mm, and internal diameter is 10~50mm, with a thickness of 1
~3mm, relative density are 95%~99.8%.
Further, solid electrolyte includes the Li of NASICON structure2O-Al2O3-MO2-P2O5(LAMP, wherein M=Ge,
Ti, Hf or Zr) based compound, garnet structure Li7La3Zr2O12Based compound, Li2S-P2S5Base binary and ternary compound,
Li2S-SiS2Base binary and ternary compound, Li2S-GeS2At least one of base binary and ternary compound.
Preferably, adhesive include paraffin, polystyrene, phenolic resin, cellulose esters, polyvinyl alcohol, in epoxy resin
At least one.
The present invention also provides the preparation methods of tubular ceramic film, include the following steps:
S1. tubulose ceramic membrane raw material is mixed according to the proportion；
S2. preformed blank is prepared, preparation method includes one of isostatic pressing, injection forming or extrusion forming；
S3. preformed blank is heat-treated, cooling polishing.
Further, when using isostatic pressing to prepare preformed blank in step S2, pressure is 150~350MPa；
Further, in step S3 heat treatment process be 300~1300 DEG C of 6~10h of roasting, heating rate for 1~2 DEG C/
min；Guarantee the microstructure of tubular ceramic membrane material it is anticipated that variation, element react to each other by control roasting heating rate
Specific granular core is formed, forms dense uniform with particle in temperature elevated structure, and keeps calcining time 6~10h energy
It is enough further ensured that the particle to be formed is relatively large, and removes impurity unstable in material to which resistivity raising be effectively reduced
Conductivity.
Further, the incubation step before heat treatment further includes roasting in step S3, process are from room temperature to 600
~650 DEG C of 1.5~2h of heat preservation, heating rate are 2~3 DEG C/min；When preparing the tubular ceramic film of specific length and thickness,
Heat preservation before roasting can make green body bulk temperature uniformity and be conducive to guarantee that the material of tubular ceramic film is heated evenly
Component reaction forms expected space structure when roasting.
Further, in step S3 when maturing temperature is higher than 900 DEG C, cooling procedure is to be down to 600 DEG C by maturing temperature,
Rate of temperature fall is 1~2 DEG C/min, then furnace cooling；When maturing temperature is lower than 900 DEG C (including 900 DEG C), furnace cooling is
It can.When temperature is higher, microstructure is still unstable in material, needs to keep the microstructure formed when roasting not to be damaged therefore
Control rate of temperature fall.
The advantages of the present invention: using solid electrolyte as tubular ceramic film raw material, it is prepared into tubulose pottery
Porcelain film is different from stacked ceramic membrane in the prior art, and the total ionic conductivity of room temperature is more than 1 × 10-4S/cm, 100~150
DEG C total ionic conductivity is 1 × 10-2S/cm or more；Tubular ceramic is obtained using the preforming rear preparation method being heat-treated simultaneously
Film, method is simple to operation, wherein preformed blank can obtain the tubular film green body of expected specification first, fits through control
Heat treatment process guarantees tubular ceramic film blank forming.
Detailed description of the invention
Fig. 1 is the object phasor of tubular ceramic film in the embodiment of the present invention 1；
Fig. 2 is temperature-ionic conductivity figure of tubular ceramic film in the embodiment of the present invention 1；
Fig. 3 is the object phasor of tubular ceramic film in the embodiment of the present invention 2；
Fig. 4 is temperature-ionic conductivity figure of tubular ceramic film in the embodiment of the present invention 2；
Fig. 5 is the object phasor of tubular ceramic film in the embodiment of the present invention 3；
Fig. 6 is temperature-ionic conductivity figure of tubular ceramic film in the embodiment of the present invention 3；
Fig. 7 is the object phasor of tubular ceramic film in the embodiment of the present invention 4；
Fig. 8 is temperature-ionic conductivity figure of tubular ceramic film in the embodiment of the present invention 4；
Fig. 9 is the object phasor of tubular ceramic film in the embodiment of the present invention 5；
Figure 10 is temperature-ionic conductivity figure of tubular ceramic film in the embodiment of the present invention 5；
Wherein, temperature-ionic conductivity Range of measuring temp is -30 DEG C~150 DEG C in Examples 1 to 3, embodiment 4
Temperature-ionic conductivity Range of measuring temp is -30 DEG C~100 DEG C in~5.
Specific embodiment
The invention will be further described With reference to embodiment.Before the present invention, the prior art is for solid
The application of electrolyte is based on stacked, and correspondingly disclosed preparation method is for disk, square piece or other shapes thin slice etc.
Plane laminar product, the relatively easy maturation of preparation process, condition are easy to control, it is found by the applicant that about tubular ceramic film and its system
Preparation Method is rarely reported, the reason is that the planes laminar product such as tubular ceramic film and disk, thin slice is different, tubular ceramic film needs shape
At curved surface tubulose, and usually require that pipe range can reach 600mm, thickness can reach 1~3mm, with meet its self-supporting and
The demand of the electrode material loaded in support tube has certain structural strength, still needs under this length and thickness requirement
Guarantee ceramic membrane have good conductivity, this brings difficulty in preparation process because tubular ceramic film curved surface, length,
It is uneven that the requirement of thickness etc. and solid electrolyte block materials lacking toughness cause material composition to be easy, and tubular film is answered everywhere
Power is uneven, and roasting process forming and the formation of microstructure are also difficult to control while established structure is easily destroyed.This hair
Bright principle is as the Li using NASICON structure2O-Al2O3-MO2-P2O5(LAMP, wherein M=Ge, Ti, Hf or Zr) base
Close the Li of object, garnet structure7La3Zr2O12Based compound, Li2S-P2S5Base binary and ternary compound, Li2S-SiS2Base two
Member and ternary compound, Li2S-GeS2When the solid electrolyte of base binary and ternary compound, the tubular ceramic film of formation is prepared
Microstructure is capable of forming the channel of conduction ion such as lithium ion to obtain high ionic conductivity；And during the preparation process first
It is rear to pass through control heat treatment condition especially maturing temperature, calcining time and period heating using mold preformed tubular green body
Rate is unlikely to deform the forming of tubulose blank sintering, and has insulating process before higher temperatures roasting first is that preventing from roasting to green body preheating
Burning makes the unexpected acute variation of temperature and leads to blank cracking, second is that warm enables green body to be heated evenly internal microstructure
Edit is conducive to be further change in roasting process；Such as the Li of NASICON structure2O-Al2O3-MO2-P2O5Base chemical combination
Object controls temperature, time and roasting heating rate, maturing temperature of heat preservation etc. during heat treatment and is conducive to solid electrolyte
It uniformly arranges and forms crystal, microchannel and conductive lithium ion radius are adapted in the material formed, while being obtained by roasting
The material final structure obtained is stable, voidage is low and consistency height further ensures tubular ceramic film with macroion conduction
Rate, when green body maturing temperature, the time control it is improper, stable structure, densification and the specific material of channel sized can not be formed；And
As selection Li2S-SiS2When base binary and ternary compound are that raw material prepare tubular ceramic film, certain roasting temperature is being controlled
After degree, calcining time, pre-incubation time, heating rate and rate of temperature fall, each component is main in the tubular ceramic membrane material of formation
With total vertex [SiS4] tetrahedron stacking form exists, this form, which is capable of providing, largely for the mobile gap of ion and to be made to move
Channel becomes larger therefore can be improved conductivity, and when maturing temperature is excessively high, too low or calcining time is too long, too short can all influence
Vertex [SiS altogether4] tetrahedron stacking provisions generation to influencing conductivity.Illustrate below by way of specific embodiment of the invention
Implementation, by taking tubular ceramic film closed end is arc-shaped as an example, actually tubular ceramic film closed end can be arbitrary shape；
Preform process only enumerates isostatic pressed method, injection forming or extrusion forming be this field routine techniques according to routine operation i.e.
It can.
Embodiment 1
(1) by Li1.5Al0.5Ge1.5P3O12Solid electrolyte powder is added in molding die corresponding with the shape of pipe,
Mold is placed in pressure vessel, equal static pressure are carried out with 350MPa pressure, demoulding obtains tubulose green compact closed at one end；
(2) gained green compact are roasted, and detailed process is temperature by room temperature to 600 DEG C of holding 2h, heating rate 2
℃/min；1000 DEG C of holding 10h are warming up to by 600 DEG C later, heating rate is 1 DEG C/min；600 are cooled to by 1000 DEG C later
DEG C, rate of temperature fall is 1 DEG C/min, later furnace cooling；Tubular ceramic film inner wall and surface are processed by shot blasting；
(3) gained tube-shaped solid electrolyte matter ceramic membrane, it is closed at one end, closed end shape be it is arc-shaped, the length of pipe is
300mm, internal diameter 50mm are the object phasor of the present embodiment tubular ceramic film, as shown in Figure 2 originally with a thickness of 3mm as shown in Figure 1
Lithium ion conductivity is 2.9 × 10 to the tubular ceramic film of embodiment at room temperature-4S/cm, lithium ion conductivity can reach at 150 DEG C
To 1.1 × 10-2S/cm。
Embodiment 2
(1) by Li6.5La3Zr1.5Nb0.5O12The polyvinyl alcohol of solid electrolyte powder and 1% content is added to the shape with pipe
In the corresponding molding die of shape, mold is placed in pressure vessel, equal static pressure are carried out with 300MPa pressure, demoulding obtains an end seal
The tubulose green compact closed；
(2) gained green compact are roasted, and detailed process is temperature by room temperature to 600 DEG C of holding 2h, heating rate 2
℃/min；1300 DEG C of holding 6h are warming up to by 600 DEG C later, heating rate is 1 DEG C/min；600 are cooled to by 1300 DEG C later
DEG C, rate of temperature fall is 1 DEG C/min, later furnace cooling；Tubular ceramic film inner wall and surface are processed by shot blasting；
(3) gained tube-shaped solid electrolyte matter ceramic membrane, it is closed at one end, closed end shape be it is arc-shaped, the length of pipe is
100mm, internal diameter 30mm are illustrated in figure 3 the object phasor of the present embodiment tubular ceramic film, as shown in Figure 4 with a thickness of 1.65mm
Lithium ion conductivity is 4.6 × 10 to the tubular ceramic film of the present embodiment at room temperature-4S/cm, lithium ion conductivity at a temperature of 150 DEG C
It can achieve 2.0 × 10-2S/cm。
Embodiment 3
(1) by Li1.35Al0.35Ti1.65P3O12The cellulose esters of solid electrolyte powder and 10% content is added to and pipe
In the corresponding molding die of shape, mold is placed in pressure vessel, equal static pressure are carried out with 200MPa pressure, demoulding obtains one end
Closed tubulose green compact；
(2) gained green compact are roasted, and detailed process is temperature by room temperature to 600 DEG C of holding 2h, heating rate 2
℃/min；900 DEG C of holding 8h are warming up to by 600 DEG C later, heating rate is 1 DEG C/min；Furnace cooling；To in tubular ceramic film
Wall and surface are processed by shot blasting；
(3) gained tube-shaped solid electrolyte matter ceramic membrane, it is closed at one end, closed end shape be it is arc-shaped, the length of pipe is
600mm, internal diameter 50mm are illustrated in figure 5 the object phasor of the present embodiment tubular ceramic film with a thickness of 3mm, as shown in Figure 6 originally
Lithium ion conductivity is 4.2 × 10 to the tubular ceramic film of embodiment at room temperature-4S/cm, lithium ion conductivity can at a temperature of 150 DEG C
To reach 1.7 × 10-2S/cm。
Embodiment 4
(1) by Li10GeP2S12(5Li2S-GeS2-P2S5) solid electrolyte powder is placed in molding corresponding with the shape of pipe
In mold, mold is placed in pressure vessel, equal static pressure are carried out with 150MPa pressure, it is raw that demoulding obtains tubulose closed at one end
Base；
(2) for gained green compact in 300 DEG C of roasting 6h, heating rate is 1 DEG C/min；Furnace cooling；To tubular ceramic film inner wall
It is processed by shot blasting with surface；
(3) gained tube-shaped solid electrolyte matter ceramic membrane, it is closed at one end, closed end shape be it is arc-shaped, the length of pipe is
50mm, internal diameter 20mm are illustrated in figure 7 the object phasor of the present embodiment tubular ceramic film with a thickness of 2mm, this reality as shown in Figure 8
Applying the tubular ceramic film of example, lithium ion conductivity is 6.2 × 10 at room temperature-3S/cm, lithium ion conductivity can be at a temperature of 100 DEG C
Reach 2.0 × 10-2S/cm。
Embodiment 5
(1) by 75Li2S-24P2S5-1P2O5Solid electrolyte powder is placed in molding die corresponding with the shape of pipe, will
Mold is placed in pressure vessel, carries out equal static pressure with 150MPa pressure, demoulding obtains tubulose green compact closed at one end；
(2) for gained green compact in 300 DEG C of roasting 6h, heating rate is 1 DEG C/min, later furnace cooling；To tubular ceramic film
Inner wall and surface are processed by shot blasting；
(3) gained tube-shaped solid electrolyte matter ceramic membrane, it is closed at one end, closed end shape be it is arc-shaped, the length of pipe is
10mm, internal diameter 10mm are illustrated in figure 9 the object phasor of the present embodiment tubular ceramic film with a thickness of 1mm, as shown in Figure 10 originally
Lithium ion conductivity is 5.2 × 10 to the tubular ceramic film of embodiment at room temperature-4S/cm, lithium ion conductivity is just at a temperature of 100 DEG C
It can achieve 1.3 × 10-2S/cm。
From the test of the conductivity of embodiment 1 to 5 it can be seen that the total ionic conductivity of its room temperature of tubular ceramic film of the invention
More than 1 × 10-4S/cm, and the conductivity at 150 DEG C of embodiment 1 to 3 is more than 1.1 × 10-2S/cm, and the pipe of embodiment 4 to 5
Conductivity just alreadys exceed 1.3 × 10 at 100 DEG C of shape ceramic membrane-2S/cm illustrates that the running temperature of tubular ceramic film of the present invention is remote
Lower than 300 DEG C or more of traditional ceramics film, operation stability and safety are substantially increased.
The present embodiments relate to the material arrived, reagent and experimental facilities, are to meet battery material unless otherwise instructed
The commercial product in field.
The above is merely a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise of not departing from core of the invention technology, improvements and modifications can also be made, these improvements and modifications are also answered
Belong to scope of patent protection of the invention.With any change in the comparable meaning and scope of claims of the present invention, all
It is considered as being included within the scope of the claims.
Claims (9)
1. conducting the tubular ceramic film of ion, which is characterized in that preparing raw material includes solid electrolyte powder and adhesive, wherein
The mass percent of adhesive is 0~10%；The total ionic conductivity of tubular ceramic film room temperature is more than 1 × 10-4S/cm, 100
~150 DEG C of total ionic conductivities are 1 × 10-2S/cm or more.
2. the tubular ceramic film of conduction ion according to claim 1, which is characterized in that one end of the tubular ceramic film
Closing, length are 10~600mm, and internal diameter is 10~50mm, and with a thickness of 1~3mm, relative density is 95%~99.8%.
3. the tubular ceramic film of conduction ion according to claim 1, which is characterized in that the solid electrolyte includes
The Li of NASICON structure2O-Al2O3-MO2-P2O5The Li of based compound, garnet structure7La3Zr2O12Based compound, Li2S-
P2S5Base binary and ternary compound, Li2S-SiS2Base binary and ternary compound, Li2S-GeS2Base binary and ternary compound
At least one of；Wherein Li2O-Al2O3-MO2-P2O5M=Ge, Ti, Hf or Zr in based compound.
4. it is according to claim 1 conduction ion tubular ceramic film, which is characterized in that described adhesive include paraffin,
At least one of polystyrene, phenolic resin, cellulose esters, polyvinyl alcohol, epoxy resin.
5. the preparation method of the tubular ceramic film of the described in any item conduction ions of Claims 1 to 4, which is characterized in that including
Following steps:
S1. tubulose ceramic membrane raw material is mixed according to the proportion；
S2. preformed blank is prepared, preparation method includes one of isostatic pressing, injection forming or extrusion forming；
S3. preformed blank is heat-treated, cooling polishing.
6. the preparation method of the tubular ceramic film of conduction ion according to claim 5, which is characterized in that the step S2
When middle use isostatic pressing prepares preformed blank, pressure is 150~350MPa.
7. the preparation method of the tubular ceramic film of conduction ion according to claim 5, which is characterized in that the step S3
Middle heat treatment process is 300~1300 DEG C of 6~10h of roasting, and heating rate is 1~2 DEG C/min.
8. the preparation method of the tubular ceramic film of conduction ion according to claim 7, which is characterized in that the step S3
Middle heat treatment further includes the incubation step before roasting, and process is the heating from room temperature to 600~650 DEG C of 1.5~2h of heat preservation
Rate is 2~3 DEG C/min.
9. the preparation method of the tubular ceramic film of conduction ion according to claim 7, which is characterized in that the step S3
In when maturing temperature is higher than 900 DEG C, cooling procedure is to be down to 600 DEG C by maturing temperature, and rate of temperature fall is 1~2 DEG C/min, then
Furnace cooling；When maturing temperature is at 900 DEG C or less, furnace cooling.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613758A (en) * | 2020-04-21 | 2020-09-01 | 浙江锋锂新能源科技有限公司 | Separator without polyolefin substrate, preparation method thereof and lithium battery containing separator |
| CN111900468A (en) * | 2020-08-11 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and lithium ion battery |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117056A (en) * | 1977-02-07 | 1978-09-26 | Chloride Silent Power Limited | Production of beta-alumina ceramic articles |
| US20090081554A1 (en) * | 2005-07-01 | 2009-03-26 | National Institute For Materials Science | All-solid lithium battery |
| US20110053002A1 (en) * | 2009-09-03 | 2011-03-03 | Ngk Insulators, Ltd. | Ceramic material and preparation method therefor |
| CN103531849A (en) * | 2013-11-01 | 2014-01-22 | 国家电网公司 | Sulfide electrolyte materials, preparation method thereof and all-solid lithium secondary battery |
| US20140134504A1 (en) * | 2012-11-15 | 2014-05-15 | Jacqueline Leslie Brown | Solid ceramic electrolytes |
| CN104466239A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN104810555A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院宁波材料技术与工程研究所 | Fast ion conductor with high lithium ionic conductivity and preparation method thereof |
| CN104810545A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院宁波材料技术与工程研究所 | Phosphate lithium fast ion conductor material and preparation method thereof |
| US20150357675A1 (en) * | 2011-07-06 | 2015-12-10 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, lithium solid-state battery, and method for producing sulfide solid electrolyte material |
| CN105406118A (en) * | 2015-12-30 | 2016-03-16 | 哈尔滨工业大学 | Ceramic solid electrolyte and preparation method thereof |
| CN105742761A (en) * | 2016-02-29 | 2016-07-06 | 苏州大学 | All-solid-state lithium-air battery and preparation method and application thereof |
| US20160329598A1 (en) * | 2014-01-22 | 2016-11-10 | Schott Ag | Ion-conducting glass ceramic having garnet-like crystal structure |
| CN108063278A (en) * | 2017-11-27 | 2018-05-22 | 浙江衡远新能源科技有限公司 | A kind of all-solid lithium-ion battery and preparation method thereof |
-
2018
- 2018-05-25 CN CN201810545465.3A patent/CN110534681A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117056A (en) * | 1977-02-07 | 1978-09-26 | Chloride Silent Power Limited | Production of beta-alumina ceramic articles |
| US20090081554A1 (en) * | 2005-07-01 | 2009-03-26 | National Institute For Materials Science | All-solid lithium battery |
| US20110053002A1 (en) * | 2009-09-03 | 2011-03-03 | Ngk Insulators, Ltd. | Ceramic material and preparation method therefor |
| US20150357675A1 (en) * | 2011-07-06 | 2015-12-10 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, lithium solid-state battery, and method for producing sulfide solid electrolyte material |
| US20140134504A1 (en) * | 2012-11-15 | 2014-05-15 | Jacqueline Leslie Brown | Solid ceramic electrolytes |
| CN103531849A (en) * | 2013-11-01 | 2014-01-22 | 国家电网公司 | Sulfide electrolyte materials, preparation method thereof and all-solid lithium secondary battery |
| US20160329598A1 (en) * | 2014-01-22 | 2016-11-10 | Schott Ag | Ion-conducting glass ceramic having garnet-like crystal structure |
| CN104810555A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院宁波材料技术与工程研究所 | Fast ion conductor with high lithium ionic conductivity and preparation method thereof |
| CN104810545A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院宁波材料技术与工程研究所 | Phosphate lithium fast ion conductor material and preparation method thereof |
| CN104466239A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN105406118A (en) * | 2015-12-30 | 2016-03-16 | 哈尔滨工业大学 | Ceramic solid electrolyte and preparation method thereof |
| CN105742761A (en) * | 2016-02-29 | 2016-07-06 | 苏州大学 | All-solid-state lithium-air battery and preparation method and application thereof |
| CN108063278A (en) * | 2017-11-27 | 2018-05-22 | 浙江衡远新能源科技有限公司 | A kind of all-solid lithium-ion battery and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| KAMAYA, NORIAKI: "A lithium superionic conductor", 《NATURE MATERIALS》 * |
| 彭会芬: "Li2S-SiS2锂离子导电玻璃的制备、结构与性能", 《硅酸盐学报》 * |
| 王衍行: "硫系锂离子导电玻璃及微晶玻璃的研究", 《功能材料》 * |
| 许阳阳: "硫化物固体电解质的研究进展", 《储能科学与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111613758A (en) * | 2020-04-21 | 2020-09-01 | 浙江锋锂新能源科技有限公司 | Separator without polyolefin substrate, preparation method thereof and lithium battery containing separator |
| CN111613758B (en) * | 2020-04-21 | 2023-02-21 | 浙江锋锂新能源科技有限公司 | Separator without polyolefin substrate, preparation method thereof and lithium battery containing separator |
| CN111900468A (en) * | 2020-08-11 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and lithium ion battery |
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