CN106972195A - A kind of inorganic sulphide electrolyte and preparation method thereof - Google Patents
A kind of inorganic sulphide electrolyte and preparation method thereof Download PDFInfo
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- CN106972195A CN106972195A CN201710249898.XA CN201710249898A CN106972195A CN 106972195 A CN106972195 A CN 106972195A CN 201710249898 A CN201710249898 A CN 201710249898A CN 106972195 A CN106972195 A CN 106972195A
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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
- H01M10/056—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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
Abstract
The invention discloses a kind of inorganic sulphide electrolyte and preparation method thereof, it is characterised in that the electrolyte is Li11Al3x‑ 11P2S8+x/2Clx, wherein 3.67≤X≤ 4, and the electrical conductivity at room temperature of the electrolyte is 1.1 × 10‑3More than S/cm.The electrical conductivity at room temperature of sulfide electrolyte of the present invention is high, and its preparation method is simple, raw materials used more low price, sample sintering temperature are low, soaking time is short, saves sintering cost.
Description
Technical field
The present invention relates to electrolyte field, and in particular to a kind of inorganic sulphide electrolyte and preparation method thereof.
Background technology
Lithium rechargeable battery is current combination property most strong battery system, with operating voltage is high, specific power and ratio
Energy is big, cyclicity is good, memory-less effect and advantages of environment protection, is widely used in notebook computer, mobile communication, number
The portable electric appts such as code video camera.In recent years, with the rise in ev industry and scale energy storage field, to lithium from
The performance of sub- battery proposes higher requirement, not only needs lithium ion battery to have high energy density and power density, also
Need it that there is the features such as security performance is high, service life is long.However, current liquid lithium ionic cell can not still meet people couple
The performance requirement of lithium battery of future generation, wherein most prominent is a little that security is poor, by electrolyte reveals triggered electronics
The event of product combustion explosion happens occasionally.In addition, with electrode material side reaction can occur in charge and discharge process for electrolyte, lead
Send a telegraph tankage and irreversible decay occur, while the problems such as also bringing along leakage, flatulence.Researchers once attempted in the electrolytic solution
Add the modes such as additive to be improved organic bath, to solve the safety issue of lithium ion battery, although obtain
Certain effect, but be inherently eliminated its safety issue, the safety issue of lithium ion battery become its
Large Copacity energy storage and the biggest obstacle of electrokinetic cell application aspect.
It is to eliminate the obstacle that above lithium ion battery is applied in electronic product and automobile industry, invents safer complete solid
State lithium ion battery is extremely urgent, and all solid lithium secondary battery has the specific energy higher than conventional liquid lithium ion battery, and
Liquid electrolyte composition is not contained in battery, to solve liquid lithium ionic cell under unconventional environment issuable leakage,
The safety issue such as inflammable, explosive, it is significant.Solid electrolyte material is the core of all solid lithium secondary battery, tool
There are low electron conduction, higher ionic conductivity and low-activation energy.Only have lithium ion to flow in solid electrolyte material
Dynamic, lithium ion carries out migration conduction by the gap in electrolyte and/or VOID POSITIONS.Assembled using inorganic solid electrolyte
All-solid lithium-ion battery has wide electrochemical stability window and high security.Solid electrolyte material also rises simultaneously
Arrived the effect of barrier film, so as to simplify the structure of battery, the encapsulation without carrying out battery under protective atmosphere, reduce lithium from
The cost of manufacture of sub- battery.In addition, solid electrolyte material has higher mechanical performance, hair than solid polymer electrolyte
All-solid-state battery is opened up, variation, the miniaturization of battery product shape is also helped.
The problem of current solid electrolyte is primarily present is that ionic conductivity is too low, therefore is found with high ionic conductivity
Solid electrolyte turn into the key that can make of all-solid lithium-ion battery, instantly, by Japanese Scientists Yuki Kato et al.
The Li of preparation9.54Si1.74P1.44S11.7Cl0.3, with higher ionic conductivity, this kind of electrolyte is with before by Japanese Scientists
The Li of Noriaki Kamaya inventions10GeP2S12It is all body-centred structure for same configuration electrolyte, it is logical with the transmission of three-dimensional ion
Road.But because both electrolyte raw materials prices are high, industrial applications are restricted.
The content of the invention
To solve above-mentioned problems of the prior art, the present invention provides a kind of inorganic sulphide electrolyte and its preparation
Method, the electrical conductivity at room temperature of sulfide electrolyte of the present invention is high, and its preparation method is simple, raw materials used more low price, sample
Product sintering temperature is low, soaking time is short, saves sintering cost.
The present invention provides a kind of inorganic sulphide electrolyte, and the electrolyte is Li11Al3x-11P2S8+x/2Clx, wherein 3.67
≤X≤4。
In addition, as described above, the electrical conductivity at room temperature of the electrolyte is 1.1 × 10-3More than S/cm.
Inorganic sulphide electrolyte preparation method as described above, it is with Li2S、P2S5、AlCl3And LiCl is original
Material, and doped with ethylene carbonate.
Inorganic sulphide electrolyte preparation method as described in weighing, Li2S、P2S5、AlCl3And LiCl mol ratio
For (4x-11)：(3.8-0.7x):(3x-11):(33-8x), 3.67≤X≤4.
Preparation method as described above, wherein, ethylene carbonate is the 3%-7% of each raw material gross mass.
Preparation method as described above, it specifically includes following step：
(1) under inactive gas atmosphere, each raw material is blended in vacuum ball grinder, ball grinder is sealed；
(2) ball milling is carried out, rotating speed is 230-250r/min, every to turn 40-50 minutes, stops cooling 10 minutes, altogether ball milling 35-
45 hours；
(3) raw material of abundant ball milling is sifted out, adds into hermetically sealed can, move in tube furnace and be sintered, sintering temperature
400-600 DEG C, sintering time 8-12 hours；
(4) after cooling down, product is taken out and ethylene carbonate is added, grinding tool is added to after being well mixed and in 25-35MPa pressures
It is cold-pressed 25-35 minutes under power, obtains Solid inorganic sulfide electrolyte sheet.
For preparation method as described above, particularly preferred following step：
(1) under inactive gas atmosphere, each raw material is blended in vacuum ball grinder, ball grinder is sealed；
(2) carry out ball milling, rotating speed is 230-250r/min, every turn 40 minutes, stop cooling 10 minutes, ball milling 40 is small altogether
When；
(3) raw material of abundant ball milling is sifted out, adds into hermetically sealed can, move in tube furnace and be sintered, sintering temperature
500 DEG C, sintering time 10 hours；
(4) after cooling down, product is taken out and ethylene carbonate is added, grinding tool is added to and in 30MPa pressure after being well mixed
Lower cold pressing 30 minutes, obtains Solid inorganic sulfide electrolyte sheet.
The inorganic sulphide electrolyte that the present invention is provided can substitute traditional lithium ion liquid electrolyte, solve lithium from
The safety issue such as sub- liquid state batteries leakage, explosive, inflammable, beneficial to a large amount of productions that various electrochemical cell is miniaturized.The present invention is carried
Its electrical conductivity at room temperature of the inorganic sulphide electrolyte of confession is high, preparation technology route is simple, it is easy to mass production, and sample burns
Junction temperature is low, soaking time is short, saves sintering cost.
Embodiment
Technical scheme is described in detail with reference to embodiment, but the present invention is not limited to these embodiments, owns
The replacement of this area conventional technical means, is all protected within the scope of the present invention.
Instrument and detection device used in the present invention is as follows：
QM-3SP4 type ball mills；Tube furnace；Infrared mould；The energization chem workstation of Switzerland ten thousand；
Producer, specification and the processing method that raw material is selected in the embodiment of the present invention are as follows.Do not influenceing effect of the present invention
Under the premise of, it also can select the raw material of other producers.
Li2S(CAS：12136-58-2)：AlfaAesar Chemical Co., Ltd., purity ＞ 99.9%；
P2S5(CAS：1314-80-3)：AlfaAesar Chemical Co., Ltd., purity ＞ 99.9%；
LiCl(CAS：7447-41-8)：AlfaAesar Chemical Co., Ltd., purity ＞ 99.9%；
AlCl3(CAS：7446-70-0)：Shanghai Jing Chun Science and Technology Co., Ltd., purity ＞ 99.0%
Ethylene carbonate (CAS：96-49-1)：Shanghai Jing Chun Science and Technology Co., Ltd., purity ＞ 98.0%.
Embodiment 1
Weigh Li2S 0.3660g、P2S5 0.3541g、AlCl30.2124g, LiCl 0.0675g, take diameter 3mm's small
Raw material and bead are together added to ball grinder, sealed and in 250r/min speed by 100, ball, 10, diameter 5mm big ball
Lower ball milling 40h, wherein ball milling program are set to every work 40 minutes, stop cooling 10 minutes.
After the abundant ball milling of above raw material, take out, and sealed to one from container in glove box, put into tube furnace liter
Temperature is incubated 10h, and naturally cool to room temperature to 500 DEG C.
The sample after sintering is taken out in glove box, and weighs 0.03g ethylene carbonates, while adding to mortar, is ground
Mill makes ethylene carbonate be dispersed in inorganic sample, and aggregate sample is added to mould, vacuum bag taking-up is put into, in 30MPa
Pressure lower sheeting 30 minutes, is made electrolyte sheet.
The AC impedance of electrolyte sheet is tested with electrochemical workstation, its electrical conductivity at room temperature is calculated, as a result as under table
State shown in table 1.
Embodiment 2
Weigh Li2S 0.3683g、P2S5 0.3541g、AlCl30.2101g, LiCl 0.0637g, in addition other
Raw material and reaction condition are same as Example 1.
Embodiment 3
Weigh Li2S 0.3706g、P2S5 0.3541g、AlCl30.2080g, LiCl 0.0600g, take diameter 3mm's small
Raw material and bead are together added to ball grinder, sealed and in 230r/min speed by 100, ball, 10, diameter 5mm big ball
Lower ball milling 45h, wherein ball milling program are set to every work 50 minutes, stop cooling 10 minutes.
After the abundant ball milling of above raw material, take out, and sealed to one from container in glove box, put into tube furnace liter
Temperature is incubated 8h, and naturally cool to room temperature to 600 DEG C.
The sample after sintering is taken out in glove box, and weighs 0.069g ethylene carbonates, while adding to mortar, is ground
Mill makes ethylene carbonate be dispersed in inorganic sample, and aggregate sample is added to mould, vacuum bag taking-up is put into, in 35Mpa
Pressure lower sheeting 25 minutes, is made electrolyte sheet.
Embodiment 4
Weigh Li2S 0.169g、P2S5 0.2675g、AlCl30.0013g, LiCl 0.1543g, take diameter 3mm's small
Raw material and bead are together added to ball grinder, sealed and in 240r/min speed by 100, ball, 10, diameter 5mm big ball
Lower ball milling 35h, wherein ball milling program are set to every work 40 minutes, stop cooling 10 minutes.
After the abundant ball milling of above raw material, take out, and sealed to one from container in glove box, put into tube furnace liter
Temperature is incubated 12h, and naturally cool to room temperature to 400 DEG C.
The sample after sintering is taken out in glove box, and weighs 0.03g ethylene carbonates, while adding to mortar, is ground
Mill makes ethylene carbonate be dispersed in inorganic sample, and aggregate sample is added to mould, vacuum bag taking-up is put into, in 25MPa
Pressure lower sheeting 35 minutes, is made electrolyte sheet.
Comparative example 1
Weigh Li2S 0.3752g、P2S5 0.3541g、AlCl30.2039g, LiCl 0.0545g, in addition other
Raw material and reaction condition are same as Example 1.
Comparative example 2
Weigh Li2S 0.3802g、P2S5 0.3541g、AlCl30.1999g, LiCl 0.0495g, in addition other
Raw material and reaction condition are same as Example 1.
Comparative example 3
Weigh Li2S 0.3850g、P2S5 0.3541g、AlCl30.1961g, LiCl 0.0453g, in addition other
Raw material and reaction condition are same as Example 1.
Ac impedance measurement is carried out to the solid electrolyte sheet obtained in embodiment and comparative example, calculates normal according to following formula
Warm electrical conductivity.
Calculation formula：
Wherein, S is the area of electrolyte sheet, and L is electrolyte sheet thickness, and R is impedance value, and σ is electrical conductivity at room temperature.
Table 1
From data above, Li is used2S、P2S5、AlCl3, the electrolyte for preparing of tetra- kinds of compounds of LiCl have it is higher
Electrical conductivity, and the present invention it is raw materials used do not include noble metal Ge, therefore prepare cost decline to a great extent, therefore, the solid state electrolysis
The large-scale application for following all-solid lithium-ion battery of verifying has larger help.At the same time, we also find out when 3.67≤x≤
When 4, more excellent electrical conductivity can be obtained.And as X=4 the solid electrolyte electrical conductivity highest.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (6)
1. a kind of inorganic sulphide electrolyte, it is characterised in that the electrolyte is Li11Al3x-11P2S8+x/2Clx, wherein 3.67
≤x≤4。
2. inorganic sulphide electrolyte as claimed in claim 1, it is characterised in that the electrical conductivity at room temperature of the electrolyte is
1.1×10-3More than S/cm.
3. inorganic sulphide electrolyte preparation method as claimed in claim 1 or 2, it is characterised in that with Li2S、P2S5、
AlCl3And LiCl is raw material, and doped with ethylene carbonate.
4. inorganic sulphide electrolyte preparation method as claimed in claim 3, it is characterised in that Li2S、P2S5、AlCl3With
And LiCl mol ratio is (4x-11)：(3.8-0.7x):(3x-11):(33-8x), 3.67≤X≤4.
5. the preparation method according to claim 3 or 4, it is characterised in that ethylene carbonate is each raw material gross mass
3%-7%.
6. the preparation method as described in claim 3-5 any one, it is characterised in that specifically include following step：
(1) under inactive gas atmosphere, each raw material is blended in vacuum ball grinder, ball grinder is sealed；
(2) ball milling is carried out, rotating speed is 230-250r/min, every to turn 40-50 minutes, stops cooling 10 minutes, ball milling 35-45 is small altogether
When；
(3) raw material of abundant ball milling is sifted out, adds into hermetically sealed can, move in tube furnace and be sintered, sintering temperature 400-
600 DEG C, sintering time 8-12 hours；
(4) after cooling down, product is taken out and ethylene carbonate is added, grinding tool is added to and under 25-35MPa pressure after being well mixed
Cold pressing 25-35 minutes, obtains Solid inorganic sulfide electrolyte sheet.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137568A (en) * | 2019-04-28 | 2019-08-16 | 山东大学 | A kind of composite solid electrolyte, preparation method and all-solid-state battery system |
| CN110563013A (en) * | 2019-08-26 | 2019-12-13 | 浙江工业大学 | Ball-milling synthesis method of aluminum sulfide |
| WO2022032956A1 (en) * | 2020-08-08 | 2022-02-17 | 天目湖先进储能技术研究院有限公司 | Sulfide solid electrolyte material, gas-phase synthesis method for materials thereof and application thereof |
| CN117638268A (en) * | 2024-01-25 | 2024-03-01 | 四川新能源汽车创新中心有限公司 | Application of ester substance as surface modifier, battery pole piece and preparation method |
| CN117638268B (en) * | 2024-01-25 | 2024-04-23 | 四川新能源汽车创新中心有限公司 | Application of ester substance as surface modifier, battery pole piece and preparation method |
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| CN104025363A (en) * | 2011-11-07 | 2014-09-03 | 出光兴产株式会社 | Solid electrolyte |
| CN104377385A (en) * | 2014-09-26 | 2015-02-25 | 珠海光宇电池有限公司 | Lithium ion secondary battery composite electrolyte film, and making method and application thereof |
| CN106129465A (en) * | 2016-08-10 | 2016-11-16 | 中国科学院西安光学精密机械研究所 | A kind of fluorine doped lithium ion solid electrolyte and preparation method thereof |
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2017
- 2017-04-17 CN CN201710249898.XA patent/CN106972195A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104025363A (en) * | 2011-11-07 | 2014-09-03 | 出光兴产株式会社 | Solid electrolyte |
| CN104377385A (en) * | 2014-09-26 | 2015-02-25 | 珠海光宇电池有限公司 | Lithium ion secondary battery composite electrolyte film, and making method and application thereof |
| CN106129465A (en) * | 2016-08-10 | 2016-11-16 | 中国科学院西安光学精密机械研究所 | A kind of fluorine doped lithium ion solid electrolyte and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137568A (en) * | 2019-04-28 | 2019-08-16 | 山东大学 | A kind of composite solid electrolyte, preparation method and all-solid-state battery system |
| CN110563013A (en) * | 2019-08-26 | 2019-12-13 | 浙江工业大学 | Ball-milling synthesis method of aluminum sulfide |
| WO2022032956A1 (en) * | 2020-08-08 | 2022-02-17 | 天目湖先进储能技术研究院有限公司 | Sulfide solid electrolyte material, gas-phase synthesis method for materials thereof and application thereof |
| CN117638268A (en) * | 2024-01-25 | 2024-03-01 | 四川新能源汽车创新中心有限公司 | Application of ester substance as surface modifier, battery pole piece and preparation method |
| CN117638268B (en) * | 2024-01-25 | 2024-04-23 | 四川新能源汽车创新中心有限公司 | Application of ester substance as surface modifier, battery pole piece and preparation method |
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