CN1193821A - Solid electrolyte and preparation and uses thereof - Google Patents

Solid electrolyte and preparation and uses thereof Download PDF

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Publication number
CN1193821A
CN1193821A CN98100827A CN98100827A CN1193821A CN 1193821 A CN1193821 A CN 1193821A CN 98100827 A CN98100827 A CN 98100827A CN 98100827 A CN98100827 A CN 98100827A CN 1193821 A CN1193821 A CN 1193821A
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solid electrolyte
liclo
inorganic salts
inorganic
pegso
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CN98100827A
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CN1091306C (en
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胡树文
方世璧
李永军
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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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

A solid electrolyte is a composite system of organic electrolyte and inorganic electrolyte, which act to each other for higher ion conductivity up to 0.001 S/cm. Use of organic substance can greatly improve the machining performance of system. It can be used in lithium ion secondary battery, electrochromic device and sensors.

Description

A kind of solid electrolyte and its production and use
The present invention relates to a kind of novel solid electrolyte and its production and use, this electrolyte has the ionic conductance height, machining property is good, safety.Leak free advantage.At lithium rechargeable battery, aspects such as electrochromic device and transducer are expected to replace traditional liquid electrolyte, are with a wide range of applications.
Solid electrolyte is the general name of ionic conductivity solid, it have safe in utilization, do not have to leak advantage such as pollution-free, that self discharge is few and the life-span is long.In energy problem serious day by day today, it has more and more caused people's extensive interest.Discover that the composite inorganic electrolyte has higher ionic conductance, as AlCl 3-LiClO 4The room-temperature ion conductivity of compound system reaches 10 -2.3S/cm.Research also shows, the compound crystalline structure that can destroy single inorganic salts of inorganic salts reduces the electrolytical fusing point of inorganic salts, make inorganic cation easier can break away from anionic constraint and freely the motion [see C.A.Angell, nature, 362,137-139 (1993)].But its machining property is poor, and film forming is poor, thereby has limited its application in practice greatly.
The solid organic polymer electrolyte is a kind of novel solid electrolyte that just grows up in recent ten years.This family macromolecule is to be matrix with the polyethers macromolecular material, and alkali metal ion is a carrier ion.It is except the performance with general solid electrolyte, and also have outstanding feature: plasticity is strong.These characteristics have been brought two big benefits: easily process film forming, the internal resistance of cell reduces; With contacting of electrode, the electric current that discharges and recharges with increase.Yet, copolymer solid electrolyte also exists fatal shortcoming: ionic conductance is lower than the level of practical application, its main cause is along with the inorganic salt content in the polymer dielectric increases, the inorganic ions that dissociates has taken place to gather, make the effective-current subnumber descend, ionic conductance reduces [seeing United States Patent (USP) 4882243] greatly.The highest room-temperature ion conductivity of report also only reaches 10 at present -4S/cm, thus limited its application in practice greatly.
The objective of the invention is to overcome inorganic molten salt electrolyte machining property difference and the low shortcoming of polyelectrolyte intermediate ion conductivity, and the machining property that provides high ionic conductance to become reconciled.
The present invention proposes the novel solid electrolyte, the compound system formed by " organic bath (organic salt)-inorganic electrolyte (inorganic salts) ": synthesized the organic salt that has polarity gene that youngster plants different structure, then that organic salt and inorganic salts is compound, inorganic salts and the electrolytical advantages of organic polymer are got up.Utilize the interaction of organic salt and inorganic salts on the one hand, further destroy the crystal phase structure of inorganic salts, impel dissociating of inorganic salts, make its ionic conductance up to 10 -3S/cm; On the other hand, owing to used organic salt, the skeleton of organic molecule can play a part improvement system machining property simultaneously.
Solid electrolyte of the present invention (percentage by weight) composed of the following components: component 1: inorganic salts; Content: 20-90% component 2: organic salt; Content: 10-80%
Said components 1 comprises: LiClO 4, LiClO 3, LiNO 3, LiOAC, LiI, Li 2CO 3, Li 2SO 4, LiCl, LiBr, LiCF 3SO 3
Said components 2 comprises synthetic several sulfate that have polar group, sulfonate, and carbonate and quaternary ammonium salt, for example: (low) polyoxyethylene thiazolinyl lithium sulfate (PEGSO 4Li), (low) polyoxyethylene thiazolinyl sulfonic acid lithium (PEGSO 3Li), the propionic acid lithium, lithium dodecyl sulfate, nonyl phenol (low) polyoxyethylene thiazolinyl lithium sulfate, nonyl phenol (low) polyoxyethylene thiazolinyl lithium sulfate, polystyrolsulfon acid lithium, the polyvinyl alcohol lithium sulfate, polymethyl siloxane propyl group oligomerisation oxyethylene group lithium sulfate (PMSPSLi), polymethyl acid oligomer ethylene oxide is the sulfonic acid lithium, polymethyl acid oligomer ethylene oxide tetramethyl ammonium chloride.
The electrolytical preparation process of " organic salt-inorganic salts " of the present invention compound system step is in the following order carried out:
1 drying and dehydrating: the inorganic salts of SILVER REAGENT such as LiClO 3And Li 2SO 4In vacuum drying oven one by one by 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ intensification drying and dehydratings, until sample no longer till the weightlessness.
2 organic salts-inorganic salt system compound: the inorganic salts such as the LiClO that will account for 20%-90% 3The organic salt that accounts for 10-80% such as the PEGSO that cross with drying 4Li, PEGSO 3Li or PMSPSLi heating and melting, after in drying box, fully mixing, be transferred in the vacuum drying oven 120 ℃ dry down,, sample is placed in the drier cools off at last no longer till the weightlessness up to sample.
The solid electrolyte of the present invention preparation has been obtained following invention effect: the interaction that (1) makes full use of organic salt and inorganic salts has improved the room-temperature ion conductivity of solid electrolyte, has reached the peak of present non-aqueous system report; (2) the organic molecule skeleton has improved its machining property, sees Table one.This invention can be used in fields such as lithium rechargeable battery, electrochromic device and transducer.
The room-temperature ion conductivity (conductivity) of the different systems of table one and form concern LiClO 31.6 3.1 1.4 1.2 1.5 8.6 1.7 conductivity (S/cm) * 10 of content 0% 10% 20% 40% 60% 80% 100% embodiment one -5* 10 -5* 10 -7* 10 -6* 10 -5* 10 -4* 10 -42.4 3.2 2.1 1.5 2.2 5.9 1.7 conductivity (S/cm) * 10 of embodiment two -5* 10 -5* 10 -7* 10 -6* 10 -5* 10 -4* 10 -41.6 2.5 3.9 2.5 3.5 1.05 1.7 conductivity (S/cm) * 10 of embodiment three -5* 10 -5* 10 -7* 10 -6* 10 -5* 10 -3* 10 -41.7 of comparative example one-4.8 8.5 1.9 7.9 1.7 conductivity (S/cm) * 10 -7* 10 -6* 10 -5* 10 -4* 10 -4* 10 -45.01 3.16 1.25 1.61 6.3 1.58 1.7 conductivity (S/cm) * 10 of comparative example two -6* 10 -5* 10 -5* 10 -7* 10 -6* 10 -5* 10 -4
Embodiment one
LiClO 3-PEGSO 4Li: the organic salt PEGSO that selects to have high polar group 4Li and inorganic salts LiClO 3Compound, the room-temperature ion conductivity of finding system is along with LiClO 3The increase of content increases afterwards earlier and falls, and at LiClO 3Content is to reach maximum 8.6 * 10 at 80% o'clock -4S/cm has reached practical level.Embodiment two
LiClO 3-PEGSO 3Li: with organic salt PEGSO 3Li and inorganic salts LiClO 3Compound, the room-temperature ion conductivity of finding system is also at LiClO 3Content is to reach maximum 5.9 * 10 at 80% o'clock -4S/cm, but be lower than LiClO 3-PEGSO 3The ionic conductance of system.Embodiment three
PMSPSLi-LiClO 3: the methylsiloxane propyl group oligomerisation ethylene oxide lithium sulfate (PMSPSLi) and the LiClO that will have flexible chain 3After compound, its room-temperature ion conductivity is at LiClO 3Content be to reach maximum 1.05 * 10 at 80% o'clock -3S/cm, this ionic conductance also are the peaks of non-aqueous system electrolyte report, and contain 20% organic polymer, have reached practical level.Comparative example one
As a comparison, with LiClO 3And Li 2SO 4Carry out compoundly with different ratios, can find, along with LiClO 3Adding, the room-temperature ion conductivity of compound system increases gradually, and at LiClO 3Content is to reach maximum at 80% o'clock.The result shows that compound the dissociating of impelling inorganic salts of inorganic salts improved its effective-current subnumber, so its room-temperature ion conductivity increases along with the adding of second component, and has reached maximum within the specific limits.Comparative example two
PEO600-LiClO 3: as a comparison, with PEO600 and LiClO 3Compound, as can be seen, PEO600-LiClO 3The ionic conductance of system is far below PEGSO 4Li-LiClO 3The level of compound system.This has illustrated that effectively simple organic substance does not have the effect that destroys the inorganic salts crystallization, and organic salt can play destruction inorganic salts crystalline structure, the effect that impels inorganic salts to dissociate.

Claims (5)

1 one kinds of solid electrolytes are made up of inorganic electrolyte or organic bath, it is characterized in that the compound system that described solid electrolyte is made up of inorganic electrolyte and organic bath, its component and content following (percentage by weight):
Inorganic salts: 20-90%
Organic salt: 10-80%
2 according to the described a kind of solid electrolyte of claim, it is characterized in that described inorganic salts are LiClO 3Or Li 2SO 4
3 according to the described a kind of solid electrolyte of claim, it is characterized in that described organic salt is PEGSO 4Li, PEGSO 3Li or PMSPSLi.
4 according to the described a kind of method for preparing solid electrolyte of claim, it is characterized in that step is carried out in the following order:
(1) drying and dehydrating: the inorganic salts of SILVER REAGENT such as LiClO 3Or Li 2SO 4In vacuum drying oven one by one by 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ intensification drying and dehydratings;
(2) organic salt-inorganic salt system is compound: with the inorganic salts LiClO of 20-90% 3Organic salt PEGSO with 10-80% 4Li, PEGSO 3Li or PMSPSLi heating and melting after fully mixing in drying box, are transferred in the vacuum drying oven dry down at 120 ℃.
5 purposes according to the described a kind of solid electrolyte of claim is characterized in that being applied in fields such as lithium rechargeable battery, electrochromic device or transducer.
CN98100827A 1998-02-18 1998-02-18 Solid electrolyte and preparation and uses thereof Expired - Fee Related CN1091306C (en)

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CN1091306C CN1091306C (en) 2002-09-18

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102473922A (en) * 2010-01-15 2012-05-23 丰田自动车株式会社 Electrode for batteries, battery comprising the electrode for batteries, and method for producing the electrode for batteries
CN103246812A (en) * 2013-05-12 2013-08-14 无锡同春新能源科技有限公司 Radio frequency identification device (RFID) system powered by lithium ion battery and used for storing individual tuberculosis information
CN106785030A (en) * 2016-12-27 2017-05-31 深圳市星源材质科技股份有限公司 A kind of preparation method of full solid state polymer electrolyte
CN108352565A (en) * 2015-06-04 2018-07-31 离子材料公司 Lithium metal battery with solid polymer electrolyte
CN113794033A (en) * 2021-09-08 2021-12-14 大连理工大学 Diaphragm suitable for solid-state flexible chloride ion battery and preparation method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103045228B (en) * 2012-11-28 2015-03-25 宁波祢若电子科技有限公司 Electrochromic material and electrochromic device

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3680249D1 (en) * 1985-05-10 1991-08-22 Asahi Chemical Ind SECONDARY BATTERY.
CN2062501U (en) * 1990-03-07 1990-09-19 中国科学院物理研究所 Full solid lithium battery
US5153082A (en) * 1990-09-04 1992-10-06 Bridgestone Corporation Nonaqueous electrolyte secondary battery
CN1044484C (en) * 1994-07-22 1999-08-04 中国科学院物理研究所 Gel electrolyte film and its prepn. method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102473922A (en) * 2010-01-15 2012-05-23 丰田自动车株式会社 Electrode for batteries, battery comprising the electrode for batteries, and method for producing the electrode for batteries
CN103246812A (en) * 2013-05-12 2013-08-14 无锡同春新能源科技有限公司 Radio frequency identification device (RFID) system powered by lithium ion battery and used for storing individual tuberculosis information
CN108352565A (en) * 2015-06-04 2018-07-31 离子材料公司 Lithium metal battery with solid polymer electrolyte
CN106785030A (en) * 2016-12-27 2017-05-31 深圳市星源材质科技股份有限公司 A kind of preparation method of full solid state polymer electrolyte
CN106785030B (en) * 2016-12-27 2020-08-25 深圳市星源材质科技股份有限公司 Preparation method of all-solid-state polymer electrolyte
CN113794033A (en) * 2021-09-08 2021-12-14 大连理工大学 Diaphragm suitable for solid-state flexible chloride ion battery and preparation method
CN113794033B (en) * 2021-09-08 2022-05-10 大连理工大学 Diaphragm suitable for solid-state flexible chloride ion battery and preparation method

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