CN108383517A - A kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics and preparation method thereof - Google Patents
A kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009766 low-temperature sintering Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000007906 compression Methods 0.000 claims abstract description 3
- 230000006835 compression Effects 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a kind of low-temperature sintering Li Mg P O solid electrolyte ceramics and preparation method thereof.This method is first by the Li of 99.5% or more purity2CO3, ammonium polyphosphate, MgO raw materials by formula LiMg2+xP3O10+xThe composition of (x=0 0.1) weighs dispensing, mixes planetary ball mill, and pre-burned obtains single-phase powder in air after drying, and crystal structure is monocline (P21/ m), wherein lithium ion is located in the channel that magnesia octahedron and phosphorus oxygen tetrahedron are constituted, preburning powder then again with alcohol mixing planetary ball mill, powder after drying sieving, binder granulation is added, disk green compact are extruded by uniaxial compression, finally ceramiic solid electrolyte is prepared in sintering under 750 ~ 850 DEG C of air atmospheres.The present invention prepares solid electrolyte ceramic in air atmosphere using solid-phase synthesis, and step is few, and method is simple, safe and environment-friendly, it can be achieved that producing in enormous quantities.
Description
Technical field
The invention belongs to field of lithium, and in particular to a kind of low-temperature sintering Li-Mg-P-O solids stablized to lithium metal
Electrolyte and preparation method thereof.
Background technology
Lithium metal has low electrode potential and high specific discharge capacity, is ideal negative material in electrochmical power source.It will
It is next-generation high-energy density, Gao An that lithium metal is combined prepared lithium solid state battery or lithium-air battery with solid electrolyte
The important development direction of full property chemical energy storage.
To realize the solid lithium battery of high-energy density, high security, long circulation life, need to solve solid electrolytic
The technical problems such as the unstable and contact difference at matter/lithium metal interface, specifically have：Interface impedance between lithium metal and electrolyte
Greatly, cell dynamics poor performance；Under high rate charge-discharge, lithium metal volume expansion and contraction generate larger stress to interface, make
Interfacial contact further deteriorates；Lithium metal and some high-valence state metallic elements (such as Ti4+、Ge4+) solid electrolyte be in direct contact
When, high-valency metal is reduced, and generates ion-electron hybrid conductive area and low conductance by-product；Lithium metal and part consistency are not
High electrolyte crystal boundary such as Li7La3Zr2O12(LLZO) substance generates chemical reaction, generates electronic conduction phase, causes battery short circuit；
Some oxide electrolytes are largely increased manufacturing cost using rare earth element, such as LLZO, (Li, La) TiO3；Sulfide solid
Although electrolyte has high lithium ion conductivity, its poor chemical stability in air, processing condition is harsher,
And there is no solve contact problems caused by Li dendrite.
It can be realized by sputtering LiPON electrolyte and prepare total solids hull cell, but its positive and negative pole material must all be adopted
Membrane electrode is made with the methods of magnetron sputtering, pulsed laser deposition, chemical vapor deposition.To solve lithium metal and Nascion
The interfacial contact problem of electrolyte, often adds transition zone, slows down reaction between the two, but transition zone brings other to lack again
Point, if transition zone polyelectrolyte floor increases the internal resistance of cell, PEO oxidative resistances and high temperature resistant type are poor, limit making for battery
With range etc..Above-mentioned method of modifying and technical characteristic all suffer from some problems, such as：Sputtering method is of high cost, and effect is not notable；
General polymer is covered in bath surface, without really realizing the excellent compatibility of oxide electrolysis confrontation lithium metal.Cause
This find it is a kind of without valence variation element with the nonreactive solid electrolyte ceramic material of lithium metal in all-solid-state battery with non-
Often big realistic meaning.
Invention content
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the purpose of the present invention is to provide one kind being free of valence variation element
Solid ceramic electrolyte and preparation method thereof, preparation process is simple, economical and energy saving environmental protection.
The purpose of the present invention is achieved through the following technical solutions：
A kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics and preparation method thereof, include the following steps：
(1) by Li2CO3, ammonium polyphosphate, MgO press LiMg2+xP3O10+xMolecular formula dispensing mixes, wherein x=0~0.1.It will
Mixed powder, which is placed in spirit solvent, carries out ball milling, wherein ball: powder: alcohol by volume ratio is 1:1:1.1, in 550 after drying
DEG C~650 DEG C of pre-burnings 2~3 hours, ceramic powders are made；
(2) ceramic powders after pre-burning are mixed with alcohol, ball：Ceramic powders：Alcohol by volume ratio=1:1:1.1, through two
After secondary ball milling, drying, then adding additives are granulated；
(3) powder after granulation is prepared into disk green compact by uniaxial compression, finally at 775-825 DEG C, air atmosphere
Chip solid electrolyte matter ceramics are prepared in lower sintering for 2~3 hours.
Preferably, the ball milling is planetary ball mill, and rotating speed is 300 revs/min, and the time is 30~120 minutes.
Preferably, step (2) described binder is the poly-vinyl alcohol solution of mass concentration 5%, and addition quality is
LiMg2P3O10The 5%~15% of ceramic powders.
Preferably, the ceramic powders that step (1) obtains are monophase materials, and crystal structure is monocline, space group R3C,
In, lithium ion is located in the channel that magnesia octahedron and phosphorus oxygen tetrahedron are constituted.
Preferably, the chip solid electrolyte matter ceramics that step (3) obtains, do not chemically react, ion with lithium metal
Conductivity is 4~9 × 10-6S·cm-1。
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) present invention prepares solid electrolyte ceramic in air atmosphere using solid-phase synthesis, and step is few, method letter
It is single, it is safe and environment-friendly, it can be achieved that producing in enormous quantities.
(2) present invention substitutes common (NH using ammonium polyphosphate4)2HPO4Material as phosphorus source synthesis of solid electrolyte powder,
It can avoid because using (NH4)2HPO4The caking phenomenon in burn-in process is caused, to eliminate cumbersome attrition process and secondary
Burn-in process, economical and energy saving environmental protection.
(3) valence variation element is free of in the solid electrolyte material prepared by the present invention, is contacted with lithium metal and chemistry does not occur
Reaction.
(4) present invention prepare solid electrolyte ceramic can low-temperature sintering securely and reliably can be real between 750-850 DEG C
It is now extensive to make.
Description of the drawings
Fig. 1 is the XRD spectrum of sample 3.
Fig. 2 is the impedance spectrum of different samples.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Examples 1 to 3
By the Li of 99.5 or more purity2CO3, MgO, ammonium polyphosphate press LiMg2+xP3O10+xMolecular formula dispensing (as shown in table 1)
Mixing, (solvent is alcohol, ball to planetary ball mill within 30~120 minutes:Powder:Alcohol by volume ratio=1:1:1.1, rotating speed is 300 revs/min
Clock), after drying in 550~650 DEG C of air atmosphere pre-burning 2~3 hours.Wherein, planetary ball mill is the ball milling in ball grinder,
Wherein ball grinder material is polytetrafluoroethylene (PTFE), and ball-milling medium is 1mm zirconium dioxide beads, and solvent is alcohol, wherein ball:Powder:Wine
Smart volume ratio=1:1:1.1.
By the secondary planetary ball mill of the powder progress 30~120 minutes after pre-burning, (solvent is alcohol, wherein ball: powder: alcohol
=1:1:1.1, rotating speed is 300 revs/min).Powder after drying is sieved after adding binder and being granulated, then passes through single shaft
10~12mm of diameter is made in pressurization, and the cylindric green compact of 1~3mm of thickness are finally sintered 2 in 750~850 DEG C of air atmosphere
Required solid electrolyte ceramic is made, above-mentioned binder uses mass concentration molten for 5% polyvinyl alcohol within~3 hours
Liquid, dosage account for the 5~15% of powder gross mass.Sintered ceramics are monocline, space group P21/ m, wherein lithium
Ion is located in the channel that magnesia octahedron and phosphorus oxygen tetrahedron are constituted.The XRD diagram of sample 3 is as shown in Figure 1, by tying XRD
It is monocline, space group P2 that sample 3, which can be obtained, in fruit refine1/m。
The solid electrolyte ceramic that the present embodiment is obtained, is tested for the property with electrochemical workstation, and method is：Take burning
Intact sample is tied, is polished two end surfaces with sand paper, and is measured the thickness and diameter of sample, calculate sample area, be subsequently placed in
It is cleaned by ultrasonic 5min in absolute ethyl alcohol, uniformly coats graphite electrode on solid electrolyte ceramic piece two sides after drying, be fixed on folder
On tool, fixture connect electrochemical workstation test electrode both ends, test frequency be 100mHz~1MHz, be used in combination Zview into
Row the Fitting Calculation, the electric property of acquisition is as shown in Fig. 2, table 1, LiMg as can be seen from Figure 22+xP3O10+xThe impedance spectrum of ceramics meets electricity
Matter characteristic is solved, high frequency half-circle area is not complete, needs to be fitted with Zview resistivity is calculated；As can be seen from Table 1
LiMg2+xP3O10+xSerial solid electrolyte whole conductivity is in 10-6The S/cm orders of magnitude, maximum can reach 9.2 × 10-6S/cm,
It is located at forefront in the material without valence variation element, possesses applications well foreground.
The raw materials used cleaning green of solid electrolyte ceramic of gained of the invention is free of rare earth element, cheap, environment
It is friendly.Solid electrolyte ceramic sintering temperature prepared by the present invention is low, energy conservation and environmental protection.It is free of and appraises at the current rate in the electrolyte obtained
Element, contacted with lithium metal do not occur chemical reaction can be applied to lithium solid state battery.
Table 1
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (5)
1. a kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics and preparation method thereof, which is characterized in that including following step
Suddenly：
（1）By Li2CO3, ammonium polyphosphate, MgO press LiMg2+xP3O10+xMolecular formula dispensing mixes, wherein x=0 ~ 0.1, after mixing
Powder be placed in spirit solvent and carry out ball milling, wherein ball: powder: alcohol by volume ratio is 1:1:1.1, in 550 DEG C ~ 650 after drying
Ceramic powders are made in DEG C pre-burning 2 ~ 3 hours；
（2）Ceramic powders after pre-burning are mixed with alcohol, ball:Ceramic powders:Alcohol by volume ratio=1:1:1.1, through secondary ball
After mill, drying, then adding additives are granulated；
（3）By the powder after granulation by uniaxial compression, disk green compact are prepared, are finally burnt under 775-825 DEG C, air atmosphere
Knot prepares chip solid electrolyte matter ceramics for 2 ~ 3 hours.
2. a kind of new type low temperature sintering Li-Mg-P-O solid electrolyte ceramics according to claim 1 and preparation method thereof,
It is characterized in that, the ball milling is planetary ball mill, rotating speed is 300 revs/min, and the time is 30 ~ 120 minutes.
3. a kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics according to claim 1 and preparation method thereof, special
Sign is, step（2）The binder is the poly-vinyl alcohol solution of mass concentration 5%, and addition quality is LiMg2P3O10Ceramic powder
The 5% ~ 15% of end.
4. a kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics according to claim 1 and preparation method thereof, special
Sign is, step（1）Obtained ceramic powders are monophase materials, and crystal structure is monocline, space group R3C, wherein lithium ion
In the channel that magnesia octahedron and phosphorus oxygen tetrahedron are constituted.
5. a kind of low-temperature sintering Li-Mg-P-O solid electrolyte ceramics according to claim 1 and preparation method thereof, special
Sign is, step（3）Obtained chip solid electrolyte matter ceramics, do not chemically react, ionic conductivity 4 with lithium metal
~9 ✕10-6 S·cm-1。
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| CN105742622A (en) * | 2016-03-27 | 2016-07-06 | 华南理工大学 | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4322485A (en) * | 1979-06-13 | 1982-03-30 | United Kingdom Atomic Energy Authority | Preparation of materials |
| CN101786873A (en) * | 2009-01-22 | 2010-07-28 | 中国科学院上海硅酸盐研究所 | Method for preparing electrolyte ceramic membrane of lithium ion battery |
| CN104221183A (en) * | 2011-11-29 | 2014-12-17 | 康宁股份有限公司 | Reactive sintering of ceramic lithium-ion solid electrolytes |
| CN104037407A (en) * | 2014-05-22 | 2014-09-10 | 北大先行科技产业有限公司 | Lithium cobalt oxide compound material coated with lithium super-Ion conductor and preparation method thereof |
| CN105742622A (en) * | 2016-03-27 | 2016-07-06 | 华南理工大学 | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor |
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