CN102456917B - 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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CN102456917B
CN102456917B CN201110213036.4A CN201110213036A CN102456917B CN 102456917 B CN102456917 B CN 102456917B CN 201110213036 A CN201110213036 A CN 201110213036A CN 102456917 B CN102456917 B CN 102456917B
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lithium ion
solid electrolyte
electrolyte
nasicon type
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CN102456917A (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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    • 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
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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+ion works in coordination with the NASICON type solid lithium-ion electrolyte of doping
Technical field
The present invention relates to a kind of solid lithium-ion electrolyte and manufacture 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, have in global portable power source market and exceed 30,000,000,000 dollars of/year shares and the occupation rate of market far exceeding other batteries, the chemical power source [Wu Yuping most with market development prospect, Wan Chunrong, Jiang Changyin, lithium rechargeable battery, Beijing: Chemical Industry Press, 2002.].Lithium rechargeable battery major part employing both at home and abroad is liquid electrolyte at present, liquid lithium ionic cell has some unfavorable factors, as: liquid organic electrolyte may be revealed, blast at too high a temperature thus cause security incident, the occasion that some are high to security requirement cannot be applied in; Liquid electrolyte lithium ion battery ubiquity Capacity fading problem, uses after a period of time due to electrode active material dissolving in the 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 fail safe is high, substantially do not have Capacity fading, solid electrolyte also serves the effect of barrier film, simplifies the structure of battery; In addition, due to without the need to isolated air, also simplify the requirement to equipment in production process, configuration design also more convenient and flexible [Wen Zhaoyin, Zhu Xiujian, the Xu Xiaoxiong etc. of battery, the research of solid state secondary battery, the 12 Chinese solid-state ionics academic meeting paper collection, 2004.]。
In all-solid lithium-ion battery, the rate determining step that the migration rate of charge carrier in solid electrolyte is often far smaller than the ion diffusion rates in the Charger transfer of electrode surface and positive electrode and becomes in whole electrode reaction dynamics, therefore development has the inorganic solid electrolyte of higher li ionic conductivity is the key place building high performance lithium ion battery.There is the LiM of NASICON type polycrystalline 2(PO 4) 3(M=Ti, Ge, Zr) is by tetrahedron PO 4with octahedra MO 6the grid structure that (as M=Ti) forms jointly, the coordination creating structural hole and can fill, making it possible to a large amount of Li ions, is a kind of up-and-coming high-lithium ion conductivity solid electrolyte.By the replacement of aliovalent ion, introducing hole or calking lithium ion can further improve ionic conductivity [Xiaoxiong Xu, Zhaoyin Wen in the structure, ZhonghuaGu, et al., Solid State Ionics, 171 (2004), 207-212.].As the Li that [woods ancestral Zuxiang, Li Shichun, silicate journal, 9 (3), 1981,253-257.] such as woods ancestral Zuxiang, Li Shichun find 1+xti 2-xga xp 3o 12, Li 1+2xti 2-xmg xp 3o 12, Li 1+xge 2-xcrxP 3o 12, Li 1+xge 2-xal xp 3o 12, Li 1+xti 2-xin xp 3o 12etc. system, all there is higher lithium ion conductivity.Existing researcher has attempted Ga at present 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+ti is substituted Deng high price or the multiple cationic moiety of low price 4+(Ge 4+, Zr 4+) or P 5+, improve NASICON parent LiM to a certain extent 2(PO 4) 3the ionic conductivity of (M=Ti, Ge, Zr).But the normal temperature lithium ion conductivity of these systems is usually 10 -4s/cm-10 -6between S/cm, the requirement of non-film lithium ion battery to electrolytic conductivity can't be met very well.The interaction of Doped ions and matrix is very complicated, and the selection of Doped ions should meet transmission bottleneck and Li as far as possible in principle +radius size is mated, Li +, vacancy concentration weak with skeleton ionic bonding forces and Li +moderate three conditions of ratio of concentration.There is Li (I) room-Li (II) room, two kinds, Li (II) room-Li (II) room mode in the migration of lithium ion in this NASICON type solid electrolyte, and wherein one group of Li (II) room-Li (II) Void diffusing mode is intercepted by oxygen atom thus reduces ionic conductivity.Therefore the contamination studying Doped ions further has very important meaning to raising NASICON type lithium ion solid electrolyte conductivity.
Summary of the invention
Technical problem to be solved by this invention is a kind of F provided for existing background technology -, Zn 2+the NASICON type lithium ion solid electrolyte LiM that cation-anion co-doping is assorted 2(PO 4) 3.Zn 2+some substitute Mi 4+, unit mole Zn 2+2mol calking lithium ion can be produced, avoid a large amount of at a low price octahedral structure that ion brings of introducing and distort and make up due to F -the gap lithium ion quantity caused of adulterating reduces.And F -oxonium ion in Some substitute M-O octahedron, has following effect: (1) F -be the extremely strong anion of electronegativity, part replaces O 2-after add the stability of structure, decrease Li-O bond energy, reduce lithium ion and skeleton bonding force, enhance Li +transfer ability; (2) F -ionic radius is less than O 2-, therefore can reduce the steric hindrance that in one group of Li (II) room-Li (II) Void diffusing, oxonium ion causes; (3) reduce the transmission bottleneck that anion is formed, make and Li +size is mated more.The synergy of both makes the normal temperature ionic conductivity of this solid electrolyte more than 10 -4s/cm, more close to the ionic conductivity of liquid electrolyte.
The present invention reaches by the following technical solutions, and this technical scheme provides a kind of lithium ion conductivity more than 10 -4the lithium ion solid electrolyte of S/cm, 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; M is the one in Ti, Ge, Zr.
In this technical scheme, by ZnO: LiF: MO 2(M=Ti, Ge, Zr): NH 4h 2pO 4: Li 2cO 3for the ratio uniform of 0.1-0.5: 0.1-0.2: 1.5-1.9: 3.0: 0.4-0.9 (mol ratio) mixes, add 95% ethanol of 3%-9%, with the rotating speed ball milling 10-50 hour of 100-500 rev/min in ball mill, after ball milling terminates in 60 DEG C of-80 DEG C of vacuum drying ovens (vacuum degree is at 10Pa-100Pa) dry 2-10 hour, grind in alms bowl at agate after taking-up and again grind 10-30 minute, the powder after grinding makes solid electrolyte powder in 5-16 hour with the ramp of 5-30 DEG C/min to 700-1000 DEG C of insulation.This powder mixing 1-5wt% is that (this bonding agent can be PVC to bonding agent, one in PVA) under forcing press with keep under the pressure of 200-500MPa pressure 2-6 minute formed thin slice, this thin slice makes lithium ion solid electrolyte thin slice in 3-10 hour with the ramp of 10-30 DEG C/min to 800-1000 DEG C of insulation in a nitrogen atmosphere.As Fig. 1 consists 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, calculate 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 mixed, Zn 2+some substitute M 4+, a small amount of doping just more can increase the quantity of calking lithium ion, avoids the octahedral structure distortion introduced a large amount of ion at a low price and bring.And F -oxonium ion in Some substitute M-O octahedron, its strong electronegativity serves steric hindrance that in reduction one group of Li (II) room-Li (II) Void diffusing, oxonium ion causes, weak lithium ion and skeleton bonding force, enhances Li +the transmission bottleneck that transfer ability, reduction anion are formed, makes and Li +the effect that size is mated more, improves the conductivity of NASICON type solid lithium-ion electrolyte significantly.Be very beneficial for the structure of all-solid lithium-ion battery.
Accompanying drawing explanation
Fig. 1 is the AC impedance figure of lithium ion solid electrolyte thin slice under electrochemical workstation, frequency versus impedance and frequency-phase figure.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by ZnO: LiF: TiO 2: NH 4h 2pO 4: Li 2cO 3it is the ratio uniform mixing of 0.1: 0.1: 1.9: 3.0: 0.5 (mol ratio), add 95% ethanol of 3%, with the rotating speed ball milling 15 hours of 100 revs/min in ball mill, the middle drying of 60 DEG C of vacuum drying ovens (vacuum degree 20Pa) 3 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, the powder after grinding makes solid electrolyte powder in 6 hours with the ramp of 6 DEG C/min to 700 DEG C of insulations.This powder mixing 2wt% bonding agent (PVC) is to keep pressure to form thin slice in 2 minutes under forcing press under the pressure of 250MPa, this thin slice makes lithium ion solid electrolyte thin slice in 10 hours with the ramp of 10 DEG C/min to 800 DEG C of insulations in a nitrogen atmosphere.
Embodiment 2: by ZnO: LiF: GeO 2: NH 4h 2pO 4: Li 2cO 3it is the ratio uniform mixing of 0.3: 0.1: 1.7: 3.0: 0.7 (mol ratio), add 95% ethanol of 9%, with the rotating speed ball milling 45 hours of 450 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree 95Pa) 9 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, the powder after grinding makes solid electrolyte powder in 15 hours with the ramp of 25 DEG C/min to 950 DEG C of insulations.This powder mixing 5wt% bonding agent (PVC) is to keep pressure to form thin slice in 6 minutes under forcing press under the pressure of 450MPa, this thin slice makes lithium ion solid electrolyte thin slice in 10 hours with the ramp of 25 DEG C/min to 1000 DEG C of insulations in a nitrogen atmosphere.
Embodiment 3: by ZnO: LiF: ZrO 2: NH 4h 2pO 4: Li 2cO 3it is the ratio uniform mixing of 0.5: 0.2: 1.5: 3.0: 0.8 (mol ratio), add 95% ethanol of 5%, with the rotating speed ball milling 30 hours of 300 revs/min in ball mill, the middle drying of 75 DEG C of vacuum drying ovens (vacuum degree 50Pa) 6 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 20 minutes, the powder after grinding makes solid electrolyte powder in 12 hours with the ramp of 10 DEG C/min to 850 DEG C of insulations.This powder mixing 2.6wt% bonding agent (PVA) is to keep pressure to form thin slice in 4 minutes under forcing press under the pressure of 400MPa, this thin slice makes lithium ion solid electrolyte thin slice in 7 hours with the ramp of 15 DEG C/min to 900 DEG C of insulations in a nitrogen atmosphere.
Embodiment 4: by ZnO: LiF: TiO 2: NH 4h 2pO 4: Li 2cO 3it is the ratio uniform mixing of 0.4: 0.1: 1.6: 3.0: 0.8 (mol ratio), add 95% ethanol of 6%, with the rotating speed ball milling 20 hours of 350 revs/min in ball mill, the middle drying of 70 DEG C of vacuum drying ovens (vacuum degree 50Pa) 8 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 10 minutes, the powder after grinding makes solid electrolyte powder in 15 hours with the ramp of 8 DEG C/min to 800 DEG C of insulations.This powder mixing 2.6wt% bonding agent (PVA) is to keep pressure to form thin slice in 4 minutes under forcing press under the pressure of 400MPa, this thin slice makes lithium ion solid electrolyte thin slice in 3 hours with the ramp of 15 DEG C/min to 900 DEG C of insulations in a nitrogen atmosphere.
Embodiment 5: by ZnO: LiF: GeO 2: NH 4h 2pO 4: Li 2cO 3it is the ratio uniform mixing of 0.4: 0.2: 1.6: 3.0: 0.7 (mol ratio), add 95% ethanol of 7%, with the rotating speed ball milling 35 hours of 300 revs/min in ball mill, the middle drying of 75 DEG C of vacuum drying ovens (vacuum degree 60Pa) 6 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 26 minutes, the powder after grinding makes solid electrolyte powder in 12 hours with the ramp of 10 DEG C/min to 850 DEG C of insulations.This powder mixing 2.6wt% bonding agent (PVC) is to keep pressure to form thin slice in 4 minutes under forcing press under the pressure of 400MPa, this thin slice makes lithium ion solid electrolyte thin slice in 7 hours with the ramp of 15 DEG C/min to 900 DEG C of insulations in a nitrogen atmosphere.

Claims (3)

1. one kind adopts 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, M are the one in Ti, Ge, Zr.
2. lithium ion solid electrolyte according to claim 1, is characterized in that ZnO: LiF: MO 2: NH 4h 2pO 4: Li 2cO 3for the ratio uniform mixing of 0.1-0.5: 0.1-0.2: 1.5-1.9: 3.0: 0.4-0.9, wherein M is one in Ti, Ge, Zr and aforementioned proportion is all mol ratio, add 95% ethanol of 3%-9%, with the rotating speed ball milling 10-50 hour of 100-500 rev/min in ball mill.
3. lithium ion solid electrolyte according to claim 1, is characterized in that, the normal temperature lithium ion conductivity of obtained solid electrolyte flake 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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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 F-And Y3+NASICON type lithium ion solid electrolyte doped with ions in synergy manner and preparation method thereof

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