CN105140559A - Na<+> superionic conductor (NASICON) type lithium-ion solid electrolyte collaboratively doping with F<->, B<3+> and Y<3+> ions and preparation method thereof - Google Patents
Na<+> superionic conductor (NASICON) type lithium-ion solid electrolyte collaboratively doping with F<->, B<3+> and Y<3+> ions and preparation method thereof Download PDFInfo
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- CN105140559A CN105140559A CN201510459938.4A CN201510459938A CN105140559A CN 105140559 A CN105140559 A CN 105140559A CN 201510459938 A CN201510459938 A CN 201510459938A CN 105140559 A CN105140559 A CN 105140559A
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The invention relates to a Na<+> superionic conductor (NASICON) type lithium-ion solid electrolyte collaboratively doping with F<->, B<3+> and Y<3+> ions and a preparation method thereof. The stoichiometric equation of the solid electrolyte is Li<1+x+2y-z>Y<x>Zr<2-x>B<y>P<3-y>O<12-z>F<z>, wherein x is equal to 0.1 to 0.5, y is equal to 0.1 to 0.3, and z is equal to 0.1 to 0.2. The NASICON type lithium-ion solid electrolyte collaboratively doping with the F<->, B<3+> and Y<3+> ions is obtained by uniformly mixing Y(NO3)<3>.6H2O, B2O3, LiF, ZrOCl<2>.8H2O, (NH4)<2>HPO4 and LiNO3 according to a mole ratio of being (0.1-0.5):(0.05-0.15):(0.1-0.2):(1.5-1.9):(2.7-2.9):(1.1-2.0) and carrying out heating, stirring, drying, ball grinding, pressing and sintering. The normal-temperature lithium ion conductivity of a solid electrolyte slice prepared according to the method is more than 5*10<-4> S/cm.
Description
Technical field
The invention belongs to a kind of lithium ion solid electrolyte and manufacture field, be specifically related to relate to a kind of F
-, B
3+and Y
3+ion NASICON type lithium ion solid electrolyte of working in coordination with doping and preparation method thereof.
Background technology
Along with the development of society, human society is more and more strong with dependence for the demand of electric energy.The continuous exhaustion of the conventional mineral energy and the living environment of a large amount of discharges to people of carbon dioxide bring serious threat.People more and more pay attention to the exploitation to regenerative resources such as solar energy, wind energy, water conservancies.Along with the rapid expansion of China's generation of electricity by new energy scale, wind power generation, water generating, photovoltaic generation, electric power, peak load shifting, pure electric automobile is regulated to access the industrial energy storage market that will be formed more than 2,000 hundred million yuan in short-term.Now, the contradiction that electrical network and new forms of energy develop is just more and more outstanding, also more urgent to the demand of energy storage.Large-scale energy-storage system oneself through becoming the important component part of following intelligent grid, exploitation high-efficiency energy-storage technology has great social and economic effects for improving the utilization ratio of electricity generation system, power quality and the extensive use of promotion regenerative resource.In current energy storage technology, one of the technology of most industrialization promotion prospect is electrochemical energy storage technology.Electrochemical energy storage technology is own through developing the type such as lead-acid battery, nickel system battery, full vanadium flow liquid battery, lithium ion battery, sodium-ion battery.Lead-acid battery low price, technology maturation, oneself is widely used in electric power system, but it has lower specific energy and specific power, and cycle life is shorter, and there is certain environmental pollution in the fabrication process.The battery efficiency such as NI-G, ni-mh is high, have extended cycle life, but retention of charge still has much room for improvement, and oneself is limited the use of by various countries because there is heavy metal pollution.The battery system that business-like sodium-ion battery and lithium ion battery etc. are safe and reliable, specific energy density is large, have extended cycle life oneself be acknowledged as have vast potential for future development in energy reserves.
Can in charge and discharge electrochemical energy storage device in various commercialization, lithium ion battery has the highest energy density.Existing commercial li-ion battery mainly comprises two types: a kind of is the lithium ion battery of liquid electrolyte; Another is the lithium ion battery of solid electrolyte.The lithium salts of liquid electrolyte is dissolved in organic solution, and comprises several functions additive.Conventional lithium salts is LiPF
6, LiFSI etc.; Organic solvent is cyclic carbonate (EC, PC), linear carbonate (DEC, DMC, EDC), carboxylic acid esters (MF, MA, EA, MP etc.).But lithium ion battery liquid organic electrolyte system, there is leakage, Yi Ran, explosive, perishable, the requirement that is not well positioned to meet following pure electric automobile and intelligent grid, battery sealing-performance is bad, can cause the potential safety hazards such as leakage inflatable.
In order to solve safety problem, current electrolysis liquid is towards solid-state future development.Substitute in the process of organic liquid electrolyte at solid electrolyte, conventional lithium ion battery energy density is on the low side to be expected to improve with these two key issues partially short in useful life, and this meets the developing direction of following energy storage power supply.
The solid electrolyte that current commercialization uniquely uses is Li
1.3al
0.3ti
1.7(PO
4)
3, but due to the problem of appraising at the current rate of Ti, make it be restricted when applying, and be similarly the LiZr of NASICON (Fast ion conductor) system
2(PO
4)
3just there is not the problem of appraising at the current rate.LiZr
2(PO
4)
3only that water chestnut side's phase time just has high conductivity and (is about 1 × 10
-5s/cm), when lower than 50 DEG C, meet and be transformed into three monoclinic phases in water chestnut side, conductivity degradation, is only 1 × 10
-8about S/cm.Therefore how LiZr is made
2(PO
4)
3water chestnut side's phase structure at normal temperatures stable existence seem highly significant.
Summary of the invention
Technical problem to be solved by this invention is a kind of F provided for existing background technology
-, B
3+and Y
3+the NASICON type lithium ion solid electrolyte LiZr that cation-anion co-doping is assorted
2(PO
4)
3, Y
3+some substitute Zr
4+, unit mole Y
3+3mol 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.B
3+some substitute P
5+except increasing calking lithium from quantity, because of the B-O bond energy large (about 523kJ/mol, more than P-O and Si-O bond energy) of the little formation of its ionic radius, polyanion covalency is strong, weak to lithium ion active force in lattice, and lithium ion mobility ability strengthens.And F
-oxonium ion in Some substitute M-O octahedron, has a 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 this three makes the normal temperature ionic conductivity of this solid electrolyte more than 5 × 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 5 × 10
-4the lithium ion solid electrolyte of S/cm, its stoichiometric equation is Li
l+x+2y-zy
xzr
2-xb
yp
3-yo
12- zf
z, in: x=0.1-0.5; Y=0.1-0.3; Z=0.1-0.2.
In technical solution of the present invention, by Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for (0.1-0.5): (0.05-0.15): (0.1-0.2): (1.5-1.9): (2.7-2.9): the ratio uniform mixing of (1.1-2.0) (mol ratio), put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 60 DEG C-90 DEG C adds thermal agitation 10-30h, oven dry obtains presoma, 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 l0Pa-100Pa) dry 5-15 hour, grind in alms bowl at agate after taking-up and again grind 30-60 minute, powder after grinding makes solid electrolyte powder in 10-30 hour with the ramp of 3-5 DEG C/min to 900-1200 DEG C of insulation.This powder is mixed in keep under the pressure of 200-500MPa forming thin slice in pressure 2-6 minute under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 10-30 hour with the ramp of 3-5 DEG C/min to 800-1210 DEG C of insulation.As Fig. 1 consists of Li
l.2y
0.1zr
1.9b
0.1p
2.9o
11.9f
0.1, solid electrolyte sheet is AC impedance figure under electrochemical workstation, and from figure, calculate conductivity is 5.2 × 10
-4s/cm.
Compared with prior art, the invention has the advantages that:
Adopt F
-, B
3+, Y
3+cation-anion co-doping is mixed, Y
3+some substitute Zr
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.B
3+some substitute P
5+except increasing calking lithium from quantity, because of the B-O bond energy large (about 523kJ/mol, more than P-O and Si-O bond energy) of the little formation of its ionic radius, polyanion covalency is strong, weak to lithium ion active force in lattice, and lithium ion mobility ability strengthens.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, reduces 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.The synergy of this three improves the conductivity of NASICON type lithium ion solid 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 prepared by the embodiment of the present invention 1;
Fig. 2 is the frequency impedance figure of lithium ion solid electrolyte thin slice under electrochemical workstation prepared by the embodiment of the present invention 1;
Fig. 3 is the frequency plot figure of lithium ion solid electrolyte thin slice under electrochemical workstation prepared by the embodiment of the present invention 1;
Fig. 4 is the AC impedance figure of lithium ion solid electrolyte thin slice under electrochemical workstation prepared by the embodiment of the present invention 4;
Fig. 5 is the AC impedance figure of lithium ion solid electrolyte thin slice under electrochemical workstation prepared by the embodiment of the present invention 4;
Fig. 6 is the X ray diffracting spectrum of lithium ion solid electrolyte thin slice prepared by the embodiment of the present invention 5.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
In this embodiment, will
Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for the ratio uniform of 0.1:0.05:0.1:1.9:2.9:1.2 (mol ratio) mixes, put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 60 DEG C adds thermal agitation 10h, oven dry obtains presoma, with the rotating speed ball milling 10 hours of 100 revs/min in ball mill, the middle drying of 60 DEG C of vacuum drying ovens (vacuum degree is at 60Pa) 5 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 30 minutes, powder after grinding makes solid electrolyte powder in 10 hours with the ramp of 3 DEG C/min to 900 DEG C of insulations, its chemical formula is Li
l.2y
0.1zr
1.9b
0.1p
2.9o
11.9f
0.1.This powder is mixed in keep pressure to form thin slice in 2 minutes under the pressure of 200MPa under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 10 hours with the ramp of 3 DEG C/min to 1210 DEG C of insulations.Detecting this lithium ion solid electrolyte thin slice, is the AC impedance figure of solid electrolyte under electrochemical workstation as shown in Figure 1, Figure 2, Figure 3 shows, and can calculate conductivity from Fig. 1 is 5.2 × 10
-4s/cm.Comparatively LiZr
2(PO
4)
3when three monoclinic phases, conductivity (is about 1 × 10
-5s/cm) high a lot.
Embodiment 2:
In this embodiment,
By Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for the ratio uniform of 0.1:0.1:0.1:1.9:2.8:1.4 (mol ratio) mixes, put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 80 DEG C adds thermal agitation 20h, oven dry obtains presoma, with the rotating speed ball milling 20 hours of 200 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree is at 100Pa) 10 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 60 minutes, powder after grinding makes solid electrolyte powder in 10 hours with the ramp of 5 DEG C/min to 1000 DEG C of insulations, its chemical formula is Li
l.4y
0.1zr
1.9b
0.2p
2.8o
11.9f
0.1.This powder is mixed in keep pressure to form thin slice in 6 minutes under the pressure of 200MPa under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 30 hours with the ramp of 5 DEG C/min to 1210 DEG C of insulations.
Embodiment 3:
In this embodiment,
By Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for the ratio uniform of 0.1:0.15:0.1:1.9:2.7:1.6 (mol ratio) mixes, put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 70 DEG C adds thermal agitation 15h, oven dry obtains presoma, with the rotating speed ball milling 25 hours of 300 revs/min in ball mill, the middle drying of 70 DEG C of vacuum drying ovens (vacuum degree is at 90Pa) 15 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 50 minutes, powder after grinding makes solid electrolyte powder in 20 hours with the ramp of 5 DEG C/min to 1150 DEG C of insulations, its chemical formula is Li
l.6y
0.15zr
1.85b
0.3p
2.7o
11.9f
0.1.This powder is mixed in keep pressure to form thin slice in 4 minutes under the pressure of 300MPa under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 30 hours with the ramp of 5 DEG C/min to 1210 DEG C of insulations.
Embodiment 4:
In this embodiment,
By Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for the ratio uniform of 0.2:0.05:0.1:1.8:2.9:1.3 (mol ratio) mixes, put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 80 DEG C adds thermal agitation 25h, oven dry obtains presoma, with the rotating speed ball milling 10 hours of 500 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree is at 100Pa) 15 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 60 minutes, powder after grinding makes solid electrolyte powder in 20 hours with the ramp of 3 DEG C/min to 1100 DEG C of insulations, its chemical formula is Li
l.3y
0.2zr
1.8b
0.1p
2.9o
11.9f
0.1.This powder is mixed in keep pressure to form thin slice in 2 minutes under the pressure of 500MPa under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 10 hours with the ramp of 5 DEG C/min to 1210 DEG C of insulations.Detect this lithium ion solid electrolyte thin slice, be illustrated in figure 4 the AC impedance figure of solid electrolyte under electrochemical workstation, can calculate conductivity from figure is 5.5 × 10
-4s/cm.
Embodiment 5:
In this embodiment,
By Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for the ratio uniform of 0.3:0.1:0.2:1.7:2.8:1.5 (mol ratio) mixes, put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 80 DEG C adds thermal agitation 20h, oven dry obtains presoma, with the rotating speed ball milling 10 hours of 400 revs/min in ball mill, the middle drying of 60 DEG C of vacuum drying ovens (vacuum degree is at 100Pa) 10 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 60 minutes, powder after grinding makes solid electrolyte powder in 10 hours with the ramp of 5 DEG C/min to 1000 DEG C of insulations, its chemical formula is Li
l.5y
0.3zr
1.7b
0.2p
2.8o
11.8f
0.2.This powder is mixed in keep pressure to form thin slice in 6 minutes under the pressure of 200MPa under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 10 hours with the ramp of 5 DEG C/min to 1210 DEG C of insulations.The crystalline structure of prepared electrolyte powder can be found out by the X ray diffracting spectrum of Fig. 6.
Embodiment 6:
In this embodiment,
By Y (NO
3)
36H
2o:B
2o
3: LiF:ZrOCl
28H
2o:(NH
4)
2hPO
4: LiNO
3for the ratio uniform of 0.5:0.15:0.2:1.5:2.7:1.9 (mol ratio) mixes, put into 150ml beaker, add the deionized water of 100ml, the magnetic force heating stirrer of 60 DEG C adds thermal agitation 20h, oven dry obtains presoma, with the rotating speed ball milling 10 hours of 400 revs/min in ball mill, the middle drying of 80 DEG C of vacuum drying ovens (vacuum degree is at 900Pa) 5 hours after ball milling terminates, grind in alms bowl at agate after taking-up and again grind 60 minutes, powder after grinding makes solid electrolyte powder in 10 hours with the ramp of 3 DEG C/min to 1200 DEG C of insulations, its chemical formula is Li
l.9y
0.5zr
1.5b
0.3p
2.7o
11.8f
0.2.This powder is mixed in keep pressure to form thin slice in 2 minutes under the pressure of 300MPa under forcing press, and this thin slice is making lithium ion solid electrolyte thin slice in 10 hours with the ramp of 3 DEG C/min to 1200 DEG C of insulations.Detect this lithium ion solid electrolyte thin slice, be illustrated in figure 5 the AC impedance figure of solid electrolyte under electrochemical workstation, can calculate conductivity from figure is 5.0 × 10
-4s/cm.
Claims (6)
1. a F
-, B
3+and Y
3+ion works in coordination with the NASICON type lithium ion solid electrolyte of doping, it is characterized in that: lithium ion solid electrolyte stoichiometric equation is Li
l+x+2y-zy
xzr
2-xb
yp
3-yo
12-zf
z,
Wherein: x=0.1-0.5; Y=0.1-0.3; Z=0.1-0.2.
2. F according to claim 1
-, B
3+and Y
3+ion works in coordination with the NASICON type lithium ion solid electrolyte of doping, it is characterized in that: x=0.1; Y=0.1; Z=0.1.
3., based on the preparation method of arbitrary lithium ion solid electrolyte of claim 1-2, it is characterized in that, comprise the following steps:
1] by Y (NO
3)
36H
2o, B
2o
3, LiF, zirconates, (NH
4)
2hPO
4and LiNO
3it is (0.1-0.5) according to mol ratio: (0.05-0.15): (0.1-0.2): (1.5-1.9): (2.7-2.9): the ratio uniform mixing of (1.1-2.0);
2] put into beaker, add deionized water, after on the magnetic force heating stirrer of 60 DEG C-90 DEG C, add thermal agitation 10-30h, dry obtain presoma;
3] by presoma in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min;
4] ball milling terminate after in 60 DEG C of-80 DEG C of vacuum drying ovens dry 5-15 hour, the vacuum degree in baking oven is l0Pa-100Pa;
5] grind in alms bowl at agate after taking out from baking oven and again grind 30-60 minute, the powder after grinding is with the ramp of 3-5 DEG C/min to 900-1200 DEG C, and solid lithium ion electrolyte powder is made in rear insulation for 10-30 hour.
4. the preparation method of lithium ion solid electrolyte according to claim 3, is characterized in that, described zirconates is zirconium nitrate Zr (NO
3)
45H
2o, zirconium oxychloride ZrOCl
28H
2o or zirconia ZrO
2.
5., based on the preparation method of arbitrary lithium ion solid electrolyte of claim 1-2, it is characterized in that, comprise the following steps:
1] by Y (NO
3)
36H
2o, B
2o
3, LiF, zirconates, (NH
4)
2hPO
4and LiNO
3it is (0.1-0.5) according to mol ratio: (0.05-0.15): (0.1-0.2): (1.5-1.9): (2.7-2.9): the ratio uniform mixing of (1.1-2.0);
2] put into beaker, add deionized water, after on the magnetic force heating stirrer of 60 DEG C-90 DEG C, add thermal agitation 10-30h, dry obtain presoma;
3] by presoma in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min;
4] ball milling terminate after in 60 DEG C of-80 DEG C of vacuum drying ovens dry 5-15 hour, the vacuum degree in baking oven is l0Pa-100Pa;
5] grind in alms bowl at agate after taking out from baking oven and again grind 30-60 minute, the powder after grinding is with the ramp of 3-5 DEG C/min to 900-1200 DEG C, and solid lithium ion electrolyte powder is made in rear insulation for 10-30 hour;
6] by step 5) powder that obtains is mixed under forcing press to keep under the pressure of 200-500MPa forming thin slice in pressure 2-6 minute, after by thin slice with the ramp of 3-5 DEG C/min to 800-1210 DEG C, be incubated and make lithium ion solid electrolyte thin slice in 10-30 hour.
6. the preparation method of lithium ion solid electrolyte according to claim 5, is characterized in that, described zirconates is zirconium nitrate Zr (NO
3)
45H
2o, zirconium oxychloride ZrOCl
28H
2o or zirconia ZrO
2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105576289A (en) * | 2016-02-05 | 2016-05-11 | 中国科学院西安光学精密机械研究所 | F- and N3+ ion cooperatively doped lithium ion solid electrolyte and preparation method thereof |
| CN105609871A (en) * | 2016-01-22 | 2016-05-25 | 昆明理工大学 | Preparation method of sodium-ion solid electrolyte with NASICON structure |
| CN108376797A (en) * | 2018-01-12 | 2018-08-07 | 华北电力大学（保定） | Resist the solid lithium ion conductors material and preparation method of lithium metal contact reduction |
| CN108682882A (en) * | 2018-06-15 | 2018-10-19 | 东莞中子科学中心 | A kind of oxygen ion conductor and its preparation method and application |
| KR20220136713A (en) * | 2021-04-01 | 2022-10-11 | 주식회사 신한세라믹 | Method for manufacturing solid electrolyte for secondary battery by molded articles |
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| CN105609871A (en) * | 2016-01-22 | 2016-05-25 | 昆明理工大学 | Preparation method of sodium-ion solid electrolyte with NASICON structure |
| CN105576289A (en) * | 2016-02-05 | 2016-05-11 | 中国科学院西安光学精密机械研究所 | F- and N3+ ion cooperatively doped lithium ion solid electrolyte and preparation method thereof |
| CN108376797A (en) * | 2018-01-12 | 2018-08-07 | 华北电力大学（保定） | Resist the solid lithium ion conductors material and preparation method of lithium metal contact reduction |
| CN108682882A (en) * | 2018-06-15 | 2018-10-19 | 东莞中子科学中心 | A kind of oxygen ion conductor and its preparation method and application |
| KR20220136713A (en) * | 2021-04-01 | 2022-10-11 | 주식회사 신한세라믹 | Method for manufacturing solid electrolyte for secondary battery by molded articles |
| KR102546049B1 (en) | 2021-04-01 | 2023-06-22 | 주식회사 신한세라믹 | Method for manufacturing solid electrolyte for secondary battery by molded articles |
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