CN102867986B - One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 - Google Patents
One B3+, al3+, ti4+and Y3+cationic co-doped solid electrolyte Li7La3Zr2O12 Download PDFInfo
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- CN102867986B CN102867986B CN201210349524.2A CN201210349524A CN102867986B CN 102867986 B CN102867986 B CN 102867986B CN 201210349524 A CN201210349524 A CN 201210349524A CN 102867986 B CN102867986 B CN 102867986B
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Abstract
The invention relates to solid electrolyte Li7La3Zr2O12 co-doped with four groups of positive ions B<3+>, Al<3+>, Ti<4+> and Y<3+>, which is characterized by having a chemical stoichiometric equation as follows: Li7+y1+y2YxLa3-xBy1Aly2Tiy3Zr2-y1-y2-y3O12, wherein, x=0.1-0.5; y1=0.1-0.2; y2=0.1-0.2; y3=0.1-0.2. The electrolyte is obtained by mixing LiCO2, Y2O3, La2O3, B2O3, Al2O3, TiO2 and ZrO according to the molar ratio of 3.6-3.7:0.05-0.25:1.25-1.45:0.05-0.1:0.05-0.1:0.1-0.2:1.4-1.7, carrying out ball-milling, pressing and firing; and Li-ion conductivity is higher than 5*10<-4>s/cm under room temperature.
Description
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.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 [Xiaoxiong Xu, Zhaoyin Wen, ZhonghuaGu, et al., Solid State Ionics, 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.Ramaswamy Murugan 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 fast ion solid electrolyte (the Ramaswamy Murugan of the lithium of application potential, Venkataraman Thangadurai, Werner Weppner, (2007). " Fast lithium ion conduction in garnet-type Li
7la
3zr
2o
12. " Angewandte Chemie-International Edition46 (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+, Ti
4+, Y
3+the lithium ion solid electrolyte Li of four component cation codopes
7la
3zr
2o
12.Y
3+part replaces La
3+, both have similar electronic structure, but Y
3+radius is less, the Ti that same radius is less
4+part replaces Zr
4+, the Al that 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; And 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; 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+y2y
xla
3-xb
y1al
y2ti
y3zr
2-y1-y2-y3o
12wherein: x=0.1-0.5; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.2.
In this technical scheme, by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: TiO
2: ZrO
2for the ratio uniform of 3.6-3.7: 0.05-0.25: 1.25-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.2: 1.4-1.7 (mol ratio) mixes, add 95% ethanol of 2%-6%, with the rotating speed ball milling 10-20 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 10-30 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 1150-1250 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
7.2y
0.1la
2.9b
0.1al
0.1ti
0.1zr
1.7o
12solid electrolyte sheet is AC impedance figure under electrochemical workstation, and from figure, calculate conductivity is 5.7 × 10
-4s/cm.
Compared with prior art, the invention has the advantages that: adopt B
3+, Al
3+, Ti
4+, Y
3+the lithium ion solid electrolyte Li of four component cation codopes
7la
3zr
2o
12.By the Y that radius is less
3+part replaces La
3+, the Ti that radius is less
4+part replaces Zr
4+, the Al that 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; B at a low price
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; 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: TiO
2: ZrO
2it is the ratio uniform mixing of 3.6: 0.05: 1.45: 0.05: 0.05: 0.1: 1.7 (mol ratios), add 95% ethanol of 6%, 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 10Pa) 10 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, powder after grinding to 900 DEG C of insulations 6 hours, then makes solid electrolyte powder in 20 hours with the ramp of 3 DEG C/min to 1150 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 11 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: TiO
2: ZrO
2it is the ratio uniform mixing of 3.7: 0.25: 1.25: 0.1: 0.1: 0.2: 1.4 (mol ratios), add 95% ethanol of 2%, 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 95Pa) 30 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 20 minutes, powder after grinding to 780 DEG C of insulations 10 hours, then makes solid electrolyte powder in 15 hours with the ramp of 7 DEG C/min to 1200 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: TiO
2: ZrO
2it is the ratio uniform mixing of 3.64: 0.15: 1.35: 0.07: 0.07: 0.15: 1.57 (mol ratios), add 95% ethanol of 3%, with the rotating speed ball milling 15 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 10 minutes, powder after grinding to 800 DEG C of insulations 7 hours, then makes solid electrolyte powder in 12 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: TiO
2: ZrO
2it is the ratio uniform mixing of 3.64: 0.1: 1.4: 0.06: 0.08: 0.15: 1.57 (mol ratios), add 95% ethanol of 5.5%, with the rotating speed ball milling 20 hours of 390 revs/min in ball mill, the middle drying of 65 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 20 minutes, powder after grinding to 750 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 2.6wt% 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 13 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: TiO
2: ZrO
2it is the ratio uniform mixing of 3.66: 0.2: 1.3: 0.08: 0.08: 0.1: 1.58 (mol ratios), add 95% ethanol of 4%, with the rotating speed ball milling 10 hours of 200 revs/min in ball mill, the middle drying of 75 DEG C of vacuum drying ovens (vacuum degree 20Pa) 15 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, powder after grinding to 710 DEG C of insulations 10 hours, then makes solid electrolyte powder in 28 hours with the ramp of 7 DEG C/min to 1170 DEG C of insulations with the ramp of 10 DEG C/min.This powder mixing 5wt% 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+, Ti
4+, Y
3+the lithium ion solid electrolyte Li of four component cation codopes
7la
3zr
2o
12, it is characterized in that stoichiometric equation is Li
7+y1+y2y
xla
3-xb
y1al
y2ti
y3zr
2-y1-y2-y3o
12, wherein: x=0.1-0.5; Y1=0.1-0.2; Y2=0.1-0.2; Y3=0.1-0.2; Adopt and prepare with the following method: by Li
2cO
3: Y
2o
3: La
2o
3: B
2o
3: Al
2o
3: TiO
2: ZrO
2with the mol ratio Homogeneous phase mixing of 3.6-3.7: 0.05-0.25: 1.25-1.45: 0.05-0.1: 0.05-0.1: 0.1-0.2: 1.4-1.7, add 95% ethanol of 2%-6%, with the rotating speed ball milling 10-20 hour of 200-400 rev/min in ball mill.
2. lithium ion solid electrolyte Li according to claim 1
7la
3zr
2o
12, it is characterized in that the normal temperature lithium ion conductivity of the solid electrolyte flake obtained is greater than 5 × 10
-4s/cm.
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