CN102867987B - A B3+, al3+, mg2+, Y3+, F- codoped solid electrolyte Li7La3Zr2O12 - Google Patents

A B3+, al3+, mg2+, Y3+, F- codoped solid electrolyte Li7La3Zr2O12 Download PDF

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CN102867987B
CN102867987B CN201210350214.2A CN201210350214A CN102867987B CN 102867987 B CN102867987 B CN 102867987B CN 201210350214 A CN201210350214 A CN 201210350214A CN 102867987 B CN102867987 B CN 102867987B
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lithium ion
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CN102867987A (en
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水淼
杨天赐
舒杰
程亮亮
冯琳
任元龙
郑卫东
高珊
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Ningbo University
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Abstract

A kind of B 3+, Al 3+, Mg 2+, Y 3+, F -the lithium ion solid electrolyte Li of codope 7la 3zr 2o 12, it is characterized in that stoichiometric equation is Li 7+y1+y2+2y3-my xla 3-xb y1al y2mg y3zr 2-y1-y2-y3o 12-mf mwherein: x=0.1-0.3; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.3; M=0.1-0.3; By Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.25-3.85: 0.05-0.15: 1.35-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.3: 1.3-1.7: 0.1-0.3 (mol ratio), forms through ball milling, compacting, sintering; Can obtain and be greater than 5 × 10 -4the room temperature lithium ion conductivity of S/cm.

Description

A kind of B 3+, Al 3+, Mg 2+, Y 3+, F -codope solid electrolyte Li 7la 3zr 2o 12
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, andY.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.The solid lithium-ion electrolyte with Practical significance will be researched and developed in addition, require that it can have good stability (to carbon dioxide and moisture stabilization) in the environment simultaneously, in order to enable the all-solid-state battery of composition use lithium metal to have high energy density as negative pole, also wish that solid state electrolysis mass-energy is stablized lithium metal and has higher decomposition voltage.Lithium ion solid electrolyte from having report at present: LLTO (Li, La) TiO 3solid electrolyte has very high intracrystalline conductivity (10 -3about S/cm) and higher normal temperature total conductivity (10 -4s/cm-10 -5s/cm), but LLTO decomposition voltage is low, cannot form the above all-solid-state battery of discharge voltage 3.7V and unstable to lithium anode; 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 of common composition, 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 [XiaoxiongXu, ZhaoyinWen, ZhonghuaGu, etal., SolidStateIonics, 171,2004,207-212.] in the structure.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-xmgxP 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 or other are as Li 1+2x+2yal xmg yti 2-x-ysi xp 3-xo 12, Li 1+x+yal xti 2-xsi yp 3-yo 12, Li 1+xal xti 2-xp 3o 12etc. system, all there is higher lithium ion conductivity.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.NASICON system is unstable to lithium anode equally in addition.RamaswamyMurugan equals on German applied chemistry periodical, within 2007, reported a kind of novel lithium ion solid electrolyte Li 7la 3zr 2o 12its lithium ion conductivity is at normal temperatures more than 1 × 10 -4s.cm -1decomposition voltage is more than 5.5V, lithium metal can be used as negative pole, to air and moisture stabilization, a kind ofly have very much the fast ion solid electrolyte of the lithium of application potential (RamaswamyMurugan, VenkataramanThangadurai, WernerWeppner, (2007). " Fastlithiumionconductioningarnet-typeLi 7la 3zr 2o 12. " AngewandteChemie-InternationalEdition46 (41): 7778-7781.).But often to reach 5.0 × 10 in the occasion conductivity higher to current requirements -4about S/cm just can meet the needs of normal battery operation, and this solid electrolyte synthesis temperature is at about 1350 DEG C in addition, and temperature is high, and energy consumption is large.
Ion doping improves a kind of very effective mode of solid lithium ion electrolytic conductivity, but the interaction of Doped ions and matrix is very complicated, the characteristic such as size, electronic structure, electronegativity of Doped ions all has a significant impact the ion conductivity of parent, and have interaction between different Doped ions, be promote lithium ion mobility or suppress the degree of lithium ion mobility and promotion and suppression all can have very large difference along with the ionic species mixed and concentration.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.The lithium ion mobility mechanism of this solid electrolyte also not yet complete studied personnel is understood.In addition, ion doping if form eutectic solid solution, then can reduce synthesis temperature to a certain extent.Therefore the solid electrolyte of contamination to exploitation high-lithium ion conductivity studying Doped ions further has very important meaning.
Summary of the invention
Technical problem to be solved by this invention is a kind of B provided for existing background technology 3+, Al 3+, Mg 2+, Y 3+, F -ion co-doped lithium ion solid electrolyte Li 7la 3zr 2o 12.Y 3+part replaces La 3+, both have similar electronic structure, but Y 3+radius is less, the Al that same radius is less 3+part replaces Zr 4+and the B that radius is less 3+part replaces Zr 4+make the contraction distortion that La-O is octahedra and the generation of Zr-O octahedron is certain, migrating channels size is more mated with lithium ion radius and improves lithium ion conductivity; But structural aberration is excessive easily causes the change of phase and have a negative impact to lithium ion conducting.And Mg 2+radius and Zr 4+closely (0.072nm), Mg 2+part replaces Zr 4+do not cause the remarkable distortion of lattice and bring a large amount of gap lithium ions, simultaneously low price B 3+and Al 3+part replaces Zr 4+also produce extra calking lithium ion, they add in lattice the quantity of moving lithium ion and improve lithium ion conductivity; F -part replaces O 2-, F -with O 2-radius is close, but electronegativity is strong, and Lattice Contraction increases lithium ion mobility channel cross-section further, improves lithium ion mobility speed; The synergy of these factors makes the normal temperature ionic conductivity of this solid electrolyte more than 5.0 × 10 -4s/cm, more close to the ionic conductivity of liquid electrolyte.Meanwhile, boron oxide compound and other components form solid solution, can reduce this solid electrolyte synthesis temperature 100-150 DEG C.
The present invention reaches by the following technical solutions, and this technical scheme provides a kind of lithium ion conductivity more than 5.0 × 10 -4the lithium ion solid electrolyte of S/cm, its stoichiometric equation is Li 7+y1+y2+2y3-my xla 3-xb y1al y2mg y3zr 2-y1-y2-y3o 12-mf mwherein: x=0.1-0.3; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.3; M=0.1-0.3.
In this technical scheme, by Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.25-3.85: 0.05-0.15: 1.35-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.3: 1.3-1.7: 0.1-0.3 (mol ratio), add 95% ethanol of 2%-6%, with the rotating speed ball milling 10-30 hour of 200-400 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 10-20 hour, grind in alms bowl at agate after taking-up and again grind 10-30 minute, powder after grinding is incubated 5-10 hour with the ramp of 5-10 DEG C/min to 700-900 DEG C, then within 10-30 hour, make solid electrolyte powder with the ramp of 2-10 DEG C/min to 1120-1250 DEG C of insulation.This powder mixing 1-5wt% be bonding agent (this bonding agent is PVC or PVA) under forcing press with keep under the pressure of 300-500MPa pressure 2-6 minute formed thin slice, this thin slice makes lithium ion solid electrolyte thin slice in 10-20 hour with the ramp of 10-20 DEG C/min to 1200-1300 DEG C of insulation in air atmosphere.As Fig. 1 consists of Li 7.3y 0.1la 2.9b 0.1al 0.1mg 0.1zr 1.7o 11.9f 0.1solid electrolyte sheet is AC impedance figure under electrochemical workstation, and from figure, calculate conductivity is 8.9 × 10 -4s/cm.
Compared with prior art, the invention has the advantages that: adopt B 3+, Al 3+, Mg 2+, Y 3+, F -ion co-doped lithium ion solid electrolyte Li 7la 3zr 2o 12.By the Y that radius is less 3+part replaces La 3+, the Al that same radius is less 3+part replaces Zr 4+and the B that radius is less 3+part replaces Zr 4+make the contraction distortion that La-O is octahedra and the generation of Zr-O octahedron is certain, migrating channels size is more mated with lithium ion radius and improves lithium ion conductivity; By radius and Zr 4+mg closely 2+part replaces Zr 4+make to roll up gap lithium ion when structure does not significantly distort, simultaneously by low price B 3+and Al 3+part replaces Zr 4+produce extra calking lithium ion, increase and move the quantity of lithium ion in lattice and improve lithium ion conductivity; F -part replaces O 2-, F -with O 2-radius is close, but electronegativity is strong, and Lattice Contraction increases lithium ion mobility channel cross-section further, improves lithium ion mobility speed; The synergy of these factors makes the normal temperature ionic conductivity of this solid electrolyte more than 5.0 × 10 -4s/cm.Meanwhile, boron oxide compound and other components form solid solution, can reduce this solid electrolyte synthesis temperature 100-150 DEG C.
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 Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.55: 0.05: 1.45: 0.05: 0.05: 0.1: 1.7: 0.1 (mol ratio), add 95% ethanol of 2%, with the rotating speed ball milling 10 hours of 250 revs/min in ball mill, the middle drying of 60 DEG C of vacuum drying ovens (vacuum degree 20Pa) 10 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, powder after grinding to 700 DEG C of insulations 6 hours, then makes solid electrolyte powder in 10 hours with the ramp of 8 DEG C/min to 1120 DEG C of insulations with the ramp of 5 DEG C/min.This powder mixing 2wt% bonding agent PVC is to keep pressure to form thin slice in 5 minutes under forcing press under the pressure of 300MPa, this thin slice makes lithium ion solid electrolyte thin slice in 20 hours with the ramp of 12 DEG C/min to 1220 DEG C of insulations in air atmosphere.
Embodiment 2: by Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.55: 0.15: 1.35: 0.1: 0.1: 0.3: 1.3: 0.3 (mol ratio), add 95% ethanol of 6%, with the rotating speed ball milling 15 hours of 380 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree 80Pa) 15 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 10 minutes, powder after grinding to 780 DEG C of insulations 10 hours, then makes solid electrolyte powder in 15 hours with the ramp of 6 DEG C/min to 1150 DEG C of insulations with the ramp of 6 DEG C/min.This powder mixing 5wt% bonding agent PVC to keep pressure to form thin slice in 2 minutes under the pressure of 450MPa, makes lithium ion solid electrolyte thin slice in 10 hours with the ramp of 15 DEG C/min to 1280 DEG C of insulations under this thin slice air atmosphere under forcing press.
Embodiment 3: by Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.55: 0.1: 1.4: 0.075: 0.075: 0.2: 1.5: 0.2 (mol ratio), add 95% ethanol of 3%, with the rotating speed ball milling 20 hours of 300 revs/min in ball mill, the middle drying of 70 DEG C of vacuum drying ovens (vacuum degree 50Pa) 20 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 20 minutes, powder after grinding to 800 DEG C of insulations 7 hours, then makes solid electrolyte powder in 11 hours with the ramp of 2 DEG C/min to 1250 DEG C of insulations with the ramp of 9 DEG C/min.This powder mixing 1wt% bonding agent PVA is to keep pressure to form thin slice in 6 minutes under forcing press under the pressure of 300MPa, this thin slice makes lithium ion solid electrolyte thin slice in 18 hours with the ramp of 15 DEG C/min to 1300 DEG C of insulations in air atmosphere.
Embodiment 4: by Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.32: 0.08: 1.42: 0.06: 0.09: 0.12: 1.58: 0.3 (mol ratio), add 95% ethanol of 5.5%, with the rotating speed ball milling 29 hours of 200 revs/min in ball mill, the middle drying of 75 DEG C of vacuum drying ovens (vacuum degree 100Pa) 10 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 15 minutes, powder after grinding to 900 DEG C of insulations 5 hours, then makes solid electrolyte powder in 20 hours with the ramp of 9 DEG C/min to 1230 DEG C of insulations with the ramp of 5 DEG C/min.This powder mixing 2.8wt% 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 12 hours with the ramp of 20 DEG C/min to 1250 DEG C of insulations in air atmosphere.
Embodiment 5: by Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF is the ratio uniform mixing of 3.47: 0.11: 1.39: 0.09: 0.08: 0.1: 1.56: 0.2 (mol ratio), add 95% ethanol of 4%, with the rotating speed ball milling 10 hours of 200 revs/min in ball mill, the middle drying of 65 DEG C of vacuum drying ovens (vacuum degree 10Pa) 17 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, powder after grinding to 760 DEG C of insulations 10 hours, then makes solid electrolyte powder in 28 hours with the ramp of 7 DEG C/min to 1200 DEG C of insulations with the ramp of 10 DEG C/min.This powder mixing 4.6wt% bonding agent PVC is to keep pressure to form thin slice in 2 minutes under forcing press under the pressure of 500MPa, this thin slice makes lithium ion solid electrolyte thin slice in 15 hours with the ramp of 10 DEG C/min to 1200 DEG C of insulations in air atmosphere.

Claims (2)

1. a B 3+, Al 3+, Mg 2+, Y 3+, F -the Li of codope 7la 3zr 2o 12lithium ion solid electrolyte, is characterized in that stoichiometric equation is Li 7+y1+y2+2y3-my xla 3-xb y1al y2mg y3zr 2-y1-y2-y3o 12-mf m, wherein: x=0.1-0.3; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.3; M=0.1-0.3; Adopt and prepare with the following method: by Li 2cO 3: Y 2o 3: La 2o 3: B 2o 3: Al 2o 3: MgO: ZrO 2: LiF with 3.4-3.9: 0.05-0.15: 1.35-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.3: 1.3-1.7: 0.1-0.3 mol ratio Homogeneous phase mixing, add 95% ethanol of 2%-6%, with the rotating speed ball milling 10-30 hour of 200-400 rev/min in ball mill.
2. Li according to claim 1 7la 3zr 2o 12lithium ion solid electrolyte, is characterized in that the normal temperature lithium ion conductivity of the solid electrolyte flake obtained is greater than 5 × 10 -4s/cm.
CN201210350214.2A 2012-09-04 2012-09-04 A B3+, al3+, mg2+, Y3+, F- codoped solid electrolyte Li7La3Zr2O12 Expired - Fee Related CN102867987B (en)

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CN104591231B (en) * 2013-10-31 2019-04-16 中国科学院上海硅酸盐研究所 Fluorine-containing garnet structure lithium ion oxide ceramics
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
CN105140559A (en) * 2015-07-30 2015-12-09 中国科学院西安光学精密机械研究所 Na<+> superionic conductor (NASICON) type lithium-ion solid electrolyte collaboratively doping with F<->, B<3+> and Y<3+> ions and preparation method thereof
JP6663685B2 (en) * 2015-11-04 2020-03-13 日本特殊陶業株式会社 Lithium ion conductive ceramic sintered body and lithium battery
CN113130976A (en) * 2019-12-30 2021-07-16 天津国安盟固利新材料科技股份有限公司 Garnet type solid electrolyte and preparation method thereof
JP7171826B1 (en) 2021-06-02 2022-11-15 住友化学株式会社 Method for producing lithium-containing oxide and solid electrolyte
CN113937352B (en) * 2021-12-17 2022-04-22 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) Composite solid electrolyte, preparation method thereof and battery

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