CN102456917A - F<-> and Zn<2+> co-doped NASICON type solid lithium ion electrolyte - Google Patents

F<-> and Zn<2+> co-doped NASICON type solid lithium ion electrolyte Download PDF

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CN102456917A
CN102456917A CN2011102130364A CN201110213036A CN102456917A CN 102456917 A CN102456917 A CN 102456917A CN 2011102130364 A CN2011102130364 A CN 2011102130364A CN 201110213036 A CN201110213036 A CN 201110213036A CN 102456917 A CN102456917 A CN 102456917A
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lithium ion
electrolyte
ion
solid electrolyte
lithium
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CN102456917B (en
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水淼
舒杰
任元龙
徐丹
郑卫东
任政娟
王青春
黄峰涛
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Ningbo University
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Abstract

The invention relates to an F<-> and Zn<2+> co-doped NASICON type solid lithium ion electrolyte. The electrolyte is characterized in that: the electrolyte has a stoichiometric formula of Li1+2x-yZnxM2-xP3O12-yFy, wherein x=0.1-0.5; y=0.1-0.2; and M is one of Ti, Ge, and Zr. According to the invention, materials are well mixed according to a molar ratio that ZnO:LiF:MO2(M=Ti, Ge, Zr):NH4H2PO4:Li2CO3=0.1-0.5:0.1-0.2:1.5-1.9:3.0:0.4-0.9; the mixture is ball-milled, compacted, and sintered, such that the electrolyte is obtained. With the electrolyte, a room temperature lithium ion conductivity is higher than 10<-4>S/cm.

Description

A kind of F -, Zn 2+The collaborative NASICON type solid lithium-ion electrolyte that mixes of ion
Technical field
The present invention relates to a kind of solid lithium-ion electrolyte and make the field.
Background technology
Lithium ion battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density; Having the occupation rate of market that exceedes 30,000,000,000 dollars of/year shares and far surpass other batteries in global portable power source market, is chemical power source [Wu Yuping, the Wan Chunrong that has the market development prospect most; Jiang Changyin; Lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].The most of employing of lithium rechargeable battery both at home and abroad is liquid electrolyte at present; Liquid lithium ionic cell has some unfavorable factors; As: liquid organic bath possibly revealed; Thereby under too high temperature, blast and cause security incident, can't be applied in some occasions high security requirement; Liquid electrolyte lithium ion battery ubiquity circulation volume attenuation problem uses after a period of time because the dissolving of electrode active material in electrolyte, reaction and degradation failure [Z.R.Zhang, Z.L.Gong; And Y.Yang, J.Phys.Chem.B, 108; 2004,17546.].And all-solid-state battery is safe, do not have the circulation volume decay basically, and solid electrolyte has also played the effect of barrier film, has simplified the structure of battery; In addition, owing to need not secluding air, also simplified in the production process requirement to equipment; The configuration design of battery also more convenient and flexible [Wen Zhaoyin, Zhu Xiujian, Xu Xiaoxiong etc.; The research of all solid state secondary cell, the 12 Chinese solid-state ionics academic meeting paper collection, 2004.]。
In all solid state lithium ion battery; The electric charge that the migration rate of charge carrier in solid electrolyte often is far smaller than electrode surface shift and positive electrode in ions diffusion speed and become the rate determining step in the entire electrode kinetics, therefore to have the inorganic solid electrolyte of higher li ionic conductivity be the core key point that makes up high performance lithium ion battery in development.LiM with NASICON type polycrystalline 2(PO 4) 3(M=Ti, Ge are by tetrahedron PO Zr) 4With octahedra MO 6(like M=Ti) common grid structure of forming, the coordination that has produced structural hole and can fill makes and can regulate and control a large amount of Li ions, is a kind of up-and-coming high-lithium ion conductivity solid electrolyte.Through the replacement of different valency ion, introducing hole or calking lithium ion can further improve ionic conductivity [Xiaoxiong Xu, Zhaoyin Wen, ZhonghuaGu, et al., Solid State Ionics, 171 (2004), 207-212.] in structure.If LIN Zu Zu-Xiang, Li Shichun, etc. [LIN Zu Zu-Xiang, Li Shichun, Ceramic Society, 9 (3) ,1981,253-257.] Found Li 1 + x Ti 2-x Ga x P 3 O 12 , Li 1 +2 x Ti 2-x Mg x P 3 O 12 , Li 1 + x Ge 2-x CrxP 3 O 12 , Li 1 + x Ge 2-x Al x P 3 O 12 , Li 1 + x Ti 2-x In x P 3 O 12 and other systems have high lithium ion conductivity .At present existing researcher has attempted Ga 3+, Cr 3+, Sc 3+, In 3+, Al 3+, La 3+, Fe 3+, Tl 3+, Lu 3+, Y 3+, Eu 3+, In 3+, Si 4+, V 5+, Ta 5+, Nb 5+, S 6+Substitute Ti Deng high price or the multiple cationic moiety of low price 4+(Ge 4+, Zr 4+) or P 5+, improved NASICON parent LiM to a certain extent 2(PO 4) 3(M=Ti, Ge, ionic conductivity Zr).But the normal temperature lithium ion conductivity of these systems is usually 10 -4S/cm-10 -6Between the S/cm, can't finely satisfy of the requirement of non-film lithium ion battery to electrolytic conductivity.The interaction of dopant ion and matrix is very complicated, and the selection of dopant ion should be satisfied transmission bottleneck and Li as far as possible in principle +The radii size coupling, Li +With skeleton ionic bond make a concerted effort weak, vacancy concentration and Li +Moderate three conditions of the ratio of concentration.The migration of lithium ion exists Li (I) room-Li (II) room, Li (II) room-Li (II) room dual mode in this NASICON type solid electrolyte, wherein one group of Li (II) room-Li (II) thus the room migration pattern is intercepted by oxygen atom and has reduced ionic conductivity.Therefore further the kind of research dopant ion and content have very important meaning to improving NASICON type lithium ion solid electrolyte conductivity.
Summary of the invention
Technical problem to be solved by this invention is a kind of F that provides to existing background technology -, Zn 2+The NASICON type lithium ion solid electrolyte LiM that cation-anion co-doping is assorted 2(PO 4) 3Zn 2+Part substitutes Mi 4+, the mole Zn of unit 2+Can produce 2mol calking lithium ion, the octahedral structure of having avoided a large amount of ions at a low price of introducing to bring distorts and remedies because F -The gap lithium ion quantity that doping causes reduces.And F -Part has substituted the oxonium ion in the M-O octahedron, has following effect: (1) F -Be the extremely strong anion of electronegativity, part replaces O 2-After increased stability of structure, reduced the Li-O bond energy, weakened lithium ion and skeleton bonding force, strengthened Li +Transfer ability; (2) F -Ionic radius is less than O 2-, therefore can reduce the steric hindrance that oxonium ion causes in the migration of one group of Li (II) room-Li (II) room; (3) reduced the transmission bottleneck that anion forms, made and Li +Size is mated more.The two synergy makes the normal temperature ionic conductivity of this solid electrolyte surpass 10 -4S/cm is more near the ionic conductivity of liquid electrolyte.
The present invention reaches through following technical scheme, and this technical scheme provides a kind of lithium ion conductivity to surpass 10 -4The lithium ion solid electrolyte of S/cm, its stoichiometric equation are Li 1+2x-yZn xM 2-xP 3O 12-yF y, wherein: x=0.1-0.5; Y=0.1-0.2; M is Ti, Ge, a kind of among the Zr.
In this technical scheme, with ZnO: LiF: MO 2(M=Ti, Ge, Zr): NH 4H 2PO 4: Li 2CO 3Be 0.1-0.5: 0.1-0.2: 1.5-1.9: 3.0: the ratio of 0.4-0.9 (mol ratio) is evenly mixed; 95% ethanol that adds 3%-9%; In ball mill with 100-500 rev/min rotating speed ball milling 10-50 hour; Ball milling finishes the back in 60 ℃ of-80 ℃ of vacuum drying ovens (vacuum degree is at 10Pa-100Pa) dry 2-10 hour; Take out the back and grind in the alms bowl at agate and ground again 10-30 minute, the powder after the grinding is warmed up to 700-1000 ℃ of insulation with 5-30 ℃/minute speed and processed the solid electrolyte powder in 5-16 hour.This powder mixing 1-5wt% is that (this bond can be PVC to bond; A kind of among the PVA) keep-up pressure under the pressure with 200-500MPa under forcing press and formed thin slice in 2-6 minute, this thin slice is warmed up to 800-1000 ℃ of insulation with 10-30 ℃/minute speed and processed the lithium ion solid electrolyte thin slice in 3-10 hour under nitrogen atmosphere.Like Fig. 1 is to consist of Li 1.1Zn 0.1Ti 1.9P 3.0O 11.9F 0.1Solid electrolyte sheet is AC impedance figure under electrochemical workstation, and from figure, calculating conductivity is 2.3x10 -4S/cm.
Compared with prior art, the invention has the advantages that: adopt F -, Zn 2+Cation-anion co-doping is assorted, Zn 2+Part substitutes M 4+, a small amount of doping just can increase the quantity of calking lithium ion morely, avoided introducing the octahedral structure distortion that a large amount of ions at a low price bring.And F -Part has substituted the oxonium ion in the M-O octahedron, and its strong negative has played and reduced oxonium ion causes in the migration of one group of Li (II) room-Li (II) room steric hindrance, weak lithium ion and skeleton bonding force, has strengthened Li +Transfer ability, reduce the transmission bottleneck that anion forms, make and Li +Size is the effect of coupling more, has improved the conductivity of NASICON type solid lithium-ion electrolyte significantly.Be very beneficial for the structure of all solid state lithium ion battery.
Description of drawings
Fig. 1 is AC impedance figure, frequency-impedance and the frequency-phase diagram of lithium ion solid electrolyte thin slice under electrochemical workstation.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1: with ZnO: LiF: TiO 2: NH 4H 2PO 4: Li 2CO 3Be 0.1: 0.1: 1.9: the ratio of 3.0: 0.5 (mol ratio) is evenly mixed; 95% ethanol of adding 3%; In ball mill with 100 rev/mins rotating speed ball milling 15 hours; Ball milling finishes the back in 60 ℃ of vacuum drying ovens (vacuum degree 20Pa) dry 3 hours, takes out the back and grinds in the alms bowl at agate and ground again 30 minutes, and the powder after the grinding is warmed up to 700 ℃ with 6 ℃/minute speed and is incubated 6 hours and processes the solid electrolyte powder.This powder mixing 2wt% bond (PVC) keep-ups pressure under the pressure with 250MPa under forcing press and formed thin slice in 2 minutes, and this thin slice is warmed up to 800 ℃ of insulations with 10 ℃/minute speed and processed the lithium ion solid electrolyte thin slice in 10 hours under nitrogen atmosphere.
Embodiment 2: with ZnO: LiF: GeO 2: NH 4H 2PO 4: Li 2CO 3Be 0.3: 0.1: 1.7: the ratio of 3.0: 0.7 (mol ratio) is evenly mixed; 95% ethanol of adding 9%; In ball mill with 450 rev/mins rotating speed ball milling 45 hours; Ball milling finishes the back in 80 ℃ of vacuum drying ovens (vacuum degree 95Pa) dry 9 hours, takes out the back and grinds in the alms bowl at agate and ground again 30 minutes, and the powder after the grinding is warmed up to 950 ℃ with 25 ℃/minute speed and is incubated 15 hours and processes the solid electrolyte powder.This powder mixing 5wt% bond (PVC) keep-ups pressure under the pressure with 450MPa under forcing press and formed thin slice in 6 minutes, and this thin slice is warmed up to 1000 ℃ of insulations with 25 ℃/minute speed and processed the lithium ion solid electrolyte thin slice in 10 hours under nitrogen atmosphere.
Embodiment 3: with ZnO: LiF: ZrO 2: NH 4H 2PO 4: Li 2CO 3Be 0.5: 0.2: 1.5: the ratio of 3.0: 0.8 (mol ratio) is evenly mixed; 95% ethanol of adding 5%; In ball mill with 300 rev/mins rotating speed ball milling 30 hours; Ball milling finishes the back in 75 ℃ of vacuum drying ovens (vacuum degree 50Pa) dry 6 hours, takes out the back and grinds in the alms bowl at agate and ground again 20 minutes, and the powder after the grinding is warmed up to 850 ℃ with 10 ℃/minute speed and is incubated 12 hours and processes the solid electrolyte powder.This powder mixing 2.6wt% bond (PVA) keep-ups pressure under the pressure with 400MPa under forcing press and formed thin slice in 4 minutes, and this thin slice is warmed up to 900 ℃ of insulations with 15 ℃/minute speed and processed the lithium ion solid electrolyte thin slice in 7 hours under nitrogen atmosphere.
Embodiment 4: with ZnO: LiF: TiO 2: NH 4H 2PO 4: Li 2CO 3Be 0.4: 0.1: 1.6: the ratio of 3.0: 0.8 (mol ratio) is evenly mixed; 95% ethanol of adding 6%; In ball mill with 350 rev/mins rotating speed ball milling 20 hours; Ball milling finishes the back in 70 ℃ of vacuum drying ovens (vacuum degree 50Pa) dry 8 hours, takes out the back and grinds in the alms bowl at agate and ground again 10 minutes, and the powder after the grinding is warmed up to 800 ℃ with 8 ℃/minute speed and is incubated 15 hours and processes the solid electrolyte powder.This powder mixing 2.6wt% bond (PVA) keep-ups pressure under the pressure with 400MPa under forcing press and formed thin slice in 4 minutes, and this thin slice is warmed up to 900 ℃ of insulations with 15 ℃/minute speed and processed the lithium ion solid electrolyte thin slice in 3 hours under nitrogen atmosphere.
Embodiment 5: with ZnO: LiF: GeO 2: NH 4H 2PO 4: Li 2CO 3Be 0.4: 0.2: 1.6: the ratio of 3.0: 0.7 (mol ratio) is evenly mixed; 95% ethanol of adding 7%; In ball mill with 300 rev/mins rotating speed ball milling 35 hours; Ball milling finishes the back in 75 ℃ of vacuum drying ovens (vacuum degree 60Pa) dry 6 hours, takes out the back and grinds in the alms bowl at agate and ground again 26 minutes, and the powder after the grinding is warmed up to 850 ℃ with 10 ℃/minute speed and is incubated 12 hours and processes the solid electrolyte powder.This powder mixing 2.6wt% bond (PVC) keep-ups pressure under the pressure with 400MPa under forcing press and formed thin slice in 4 minutes, and this thin slice is warmed up to 900 ℃ of insulations with 15 ℃/minute speed and processed the lithium ion solid electrolyte thin slice in 7 hours under nitrogen atmosphere.

Claims (4)

1. one kind is adopted F -, Zn 2+Ion co-doped NASICON type lithium ion solid electrolyte, its stoichiometric equation is Li 1+2x-yZn xM 2-xP 3O 12-yF y, wherein: x=0.1-0.5; Y=0.1-0.2.
2. novel solid lithium-ion electrolyte according to claim 1 is characterized in that, M is Ti, Ge, a kind of among the Zr.
3. novel solid lithium-ion electrolyte according to claim 1 is characterized in that ZnO: LiF: MO 2(M=Ti, Ge, Zr): NH 4H 2PO 4: Li 2CO 3Be 0.1-0.5: 0.1-0.2: 1.5-1.9: 3.0: the ratio of 0.4-0.9 (mol ratio) is evenly mixed, and adds 95% ethanol of 3%-9%, in ball mill with 100-500 rev/min rotating speed ball milling 10-50 hour.
4. novel solid lithium-ion electrolyte according to claim 1 is characterized in that, the normal temperature lithium ion conductivity of the solid electrolyte flake that makes is greater than 10 -4S/cm.
CN201110213036.4A 2011-07-20 2011-07-20 F<-> and Zn<2+> co-doped NASICON type solid lithium ion electrolyte Expired - Fee Related CN102456917B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103943842A (en) * 2013-01-23 2014-07-23 江南大学 Synthesis of modified lithium-rich layered cathode material co-doped by anion Cl- and cation Cr<3+>
CN105070944A (en) * 2015-07-30 2015-11-18 中国科学院西安光学精密机械研究所 NASICON lithium-ion solid electrolyte synergistically doped with F<-> and Y<3+> ions and preparation method thereof

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CN101920953A (en) * 2010-06-28 2010-12-22 宁波大学 Preparation method of spherical anode material LiVPO4F

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103943842A (en) * 2013-01-23 2014-07-23 江南大学 Synthesis of modified lithium-rich layered cathode material co-doped by anion Cl- and cation Cr<3+>
CN105070944A (en) * 2015-07-30 2015-11-18 中国科学院西安光学精密机械研究所 NASICON lithium-ion solid electrolyte synergistically doped with F<-> and Y<3+> ions and preparation method thereof

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