CN112939601A - 一种电解质材料、其制备方法和应用 - Google Patents
一种电解质材料、其制备方法和应用 Download PDFInfo
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- CN112939601A CN112939601A CN202110119543.5A CN202110119543A CN112939601A CN 112939601 A CN112939601 A CN 112939601A CN 202110119543 A CN202110119543 A CN 202110119543A CN 112939601 A CN112939601 A CN 112939601A
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- 239000002001 electrolyte material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims description 67
- 239000000463 material Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000010955 niobium Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910020854 La(OH)3 Inorganic materials 0.000 claims description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical group O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910005267 GaCl3 Inorganic materials 0.000 claims description 3
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 3
- 229910002249 LaCl3 Inorganic materials 0.000 claims description 3
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910004537 TaCl5 Inorganic materials 0.000 claims description 3
- 229910003069 TeO2 Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910003091 WCl6 Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 3
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- PNCDAXYMWHXGON-UHFFFAOYSA-N ethanol;niobium Chemical compound [Nb].CCO.CCO.CCO.CCO.CCO PNCDAXYMWHXGON-UHFFFAOYSA-N 0.000 claims description 3
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 claims description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 27
- 230000008569 process Effects 0.000 abstract description 19
- 238000000227 grinding Methods 0.000 abstract description 18
- 239000002223 garnet Substances 0.000 abstract description 8
- 238000010345 tape casting Methods 0.000 abstract description 4
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 91
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 238000005056 compaction Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- 238000001238 wet grinding Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000013590 bulk material Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
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- 238000006467 substitution reaction Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
本发明公开了一种电解质材料、其制备方法和应用,属于电解质材料的技术领域。所述陶瓷材料具有3D结构,从上至下依次包括骨架层、致密层和骨架层,所述Li7La3Zr2O12体系陶瓷材料的化学通式为Li7‑3x‑y+z A x La3Zr2‑yB y O12+z/2,0<x≤0.4,0.4≤y≤0.8,0≤z≤1.4,或者化学通式为Li7‑3x‑2w+z A x La3Zr2‑wC w O12+z/2,0<x≤0.4,0.1≤w≤0.7,0≤z≤1.4。本发明只需要成型磨具、加压和热处理工艺即可实现三层固体电解质的可控制备,比流延法制备所需的工艺要求简单,可行性高,可实现大规模生产。本发明通过添加粘结剂或造孔剂这种低成本、简单的工艺方法,可以实现全固态锂金属电池在较高电流密度下的稳定循环,为石榴石基全固态锂电池的制备奠定了基础。
Description
技术领域
本发明属于电解质材料的技术领域,特别涉及一种电解质材料、其制备方法和应用。
背景技术
石榴石结构固体电解质材料是近十几年来被广泛研究的一种氧化物固体电解质材料,该体系材料具有高离子电导率的基础组分是Li7La3Zr2O12(LLZO),研究人员围绕该组分进行一系列的掺杂取代或复合的研究,目前LLZO体系的最高离子电导率可超过1mS/cm,并且表现出对金属锂的稳定性,拥有超过5V以上的电化学窗口,显示出LLZO体系应用于固态锂金属电池的巨大潜力。
在LLZO体系中,一般有立方相和四方相两种物相结构,其室温离子电导率分别可达10-4~10-3 S/cm和10-6 S/cm。因此,研究者们一般关注立方相结构LLZO体系材料。立方相结构的LLZO材料一般由LaO8十二面体和ZrO6八面体构成骨架结构,锂离子一般占据24d四面体空隙和96h八面体空隙,从而构成了锂离子传输的三维通道。一般而言,对LLZO体系的掺杂取代主要围绕Li、La、Zr位,常见的是Li位掺杂Al、Ga,Zr位掺杂Nb、Ta、W或Te等。
然而立方LLZO相一般很容易在空气中与水发生反应,在其表层形成LiOH,并进一步与空气中CO2反应生成离子电导率极低的Li2CO3(200℃下仅10-8 S/cm),且Li2CO3的氧化电位较低,只有3.2V,但其主晶相结构依旧是立方LLZO相。针对立方LLZO陶瓷块体而言,若致密度较高,则陶瓷块体表层的Li2CO3相一般不会超过100μm,通过在干燥气氛下打磨抛光处理即可除去。这说明,致密度较高的立方LLZO陶瓷块体在空气中保存并不会对其本征特性造成极大的影响。
正是因为上述Li2CO3层的存在,LLZO和金属锂负极的界面接触表现较差,根据密度泛函理论计算,Li2CO3与金属锂之间的接触角高达142°,表现出很强的疏锂特性。
发明内容
本发明为解决上述背景技术中存在的技术问题,提出一种全新3D结构的LLZO块体材料,主要通过添加造孔剂或粘结剂来实现3D结构骨架的形成,通过加压成型和后续热处理的方式最终来形成所述的3D结构LLZO块体材料。
本发明采用以下技术方案来实现:一种电解质材料,所述陶瓷材料具有3D结构,从上至下依次包括骨架层、致密层和骨架层。
在进一步的实施例中,所述陶瓷材料的化学通式为Li7-3x-y+z A x La3Zr2-yB y O12+z/2;
式中,A为三价金属元素,B为五价金属元素,0<x≤0.4,0.4≤y≤0.8,0≤z≤1.4。
在进一步的实施例中,所述陶瓷材料的化学通式为Li7-3x-2w+z A x La3Zr2-wC w O12+z/2;
式中,A为三价金属元素,C为六价金属元素,0<x≤0.4,0.1≤w≤0.7,0≤z≤1.4。
在进一步的实施例中,Li源为Li2CO3、LiOH、LiHCO3、CH3COOLi、CHOOLi、LiNO3、或其水合物中的至少一种;
“其水合物”,即上述Li源物质或其他锂源物质的水合物,下同。
La源为La2O3、La(OH)3、La2(SO4)3、乙酸镧、LaCl3、La(NO3)3、或其水合物中的至少一种;
Zr源为ZrO2、ZrCl4、ZrO(NO3)2、碱式碳酸锆、锆粉、二氢化锆、或其水合物中的至少一种。
在进一步的实施例中,所述A为Al或Ga;
其中,Al源为Al(OH)3、Al2O3、Al(PO3)3、Al(NO3)3、AlCl3、Al2(SO4)3、或其水合物中的至少一种;
Ga源为Ga2O3、GaCl3、Ga(NO3)3、Ga2(SO4)3、或其水合物中的至少一种。
在进一步的实施例中,B为Ta或Nb,其中,Ta/Nb源为Ta2O5/ Nb2O5、钽粉/铌粉、TaCl5/NbCl5、乙醇钽/乙醇铌、或其水合物中的至少一种。
在进一步的实施例中,C为W、Te,其中,W源为WO2、WO3、WCl6、钨粉、钨酸、或其水合物中的至少一种;
Te源为TeO2、碲粉、或其水合物中的至少一种。
制备如上所述的一种电解质材料的制备方法,具体包括以下步骤:
步骤一、将原材料按照合成组分所示化学式进行配比,得到混合物;
步骤二、将混合物装入混料设备中,加入弥散剂进行球磨或混合,达到混匀目的,完成后将混合物烘干;
步骤三、将烘干后的混合物放入加热设备中进行热处理,在700~950℃下热处理1~10h,得到预烧后LLZO粉体;
步骤三、将烘干后的混合物放入加热设备中进行热处理,在700~950℃下热处理1~10h,得到预烧后LLZO粉体;优选的在750~900℃下热处理2~8h,更优选的在800~850℃下热处理4~6h,最优选的在825℃下热处理5h,
步骤四、将预烧后LLZO粉体进行破碎,并进行亚微米化处理;
步骤五、按照上层为3D结构骨架层、中间为致密层、下层为3D结构骨架层的顺序铺设粉层,压制成型为固体电解质块体,并对块体进行加热处理得到到具有3D结构的LLZO体系陶瓷块体材料。
在进一步的实施例中,所述步骤四具体包括以下流程:用醇类作为弥散剂进行行星式球磨,粉体烘干后将其中一部分粉体添加粘结剂或造孔剂并混合均匀;混合有粘结剂或造孔剂的粉体,同时用于作为上层的3D结构骨架层和下层的3D结构骨架层;
粘结剂或造孔剂选用PVA、PMMA、淀粉、PVP、PEG、碳酸氢铵或尿素中的至少一种。
在进一步的实施例中,所述步骤五中的热处理采用一步处理或者两步处理;
当采用一步处理时,热处理的条件为:温度1100~1300 ℃下处理0.1~4h;
当采用两步处理时,热处理的条件为:第一步在温度1100~1300 ℃下处理0.1~1h,而后自然降温至第二步在1000~1200 ℃下处理0.1~8h。
一种电解质材料的制备方法制备出来的固体电解质材料在电池中的应用,位于上层的3D结构骨架层用于填充正极材料形成复合正极,位于下层的3D结构骨架层用则用于填充负极材料形成复合负极。
本发明的有益效果:本发明只需要成型磨具、加压和热处理工艺即可实现三层固体电解质的可控制备,比流延法制备所需的工艺要求简单,可行性高,可实现大规模生产。
本发明通过添加粘结剂或造孔剂这种低成本、简单的工艺方法,可以实现全固态锂金属电池在较高电流密度下的稳定循环,为石榴石基全固态锂电池的制备奠定了基础。
附图说明
图1为本发明的具有3D结构的LLZO体系陶瓷块体的结构示意图。
具体实施方式
下面将结合附图和实施例,对本发明技术方案进行清楚、完整的描述。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
针对背景技术中所指出的问题,为了能够更好的让LLZO块体表现出亲锂特性,目前通常的做法有以下几种:
1.在干燥环境中将LLZO块体表层的Li2CO3进行打磨抛光处理,然后在惰性气体氛围中将LLZO块体表面进行熔锂或者贴锂处理。这种操作的优点是简单,缺点是在打磨抛光中不可避免会引入新的杂质,同时LLZO块体材料属于多晶材料,如果表层没有进行结构设计,即便LLZO可以表现出较好的亲锂特性,但仍旧不能在较高充放电电流下表现出较好的循环特性。
2.在LLZO块体表层直接沉积一层亲锂的材料,如Au、Cu或者ZnO或者Al2O3等,通过沉积一层亲锂材料,可以改善LLZO块体同金属锂的接触特性,但仍旧存在第1点中描述的问题,这是由于锂负极在充放电过程中体积变化影响了界面稳定性,在较高的电流密度下很容易出现锂枝晶造成电池的短路。
3.采用酸处理LLZO块体,如ACS Energy Letters, 2020, 5, 252−262中提到,采用酸处理LLZO块体后得到具有亲锂特性的3D骨架结构LLZO块体。这种结构特征在于致密的LLZO块体层上下两侧均有被酸刻蚀后的多孔3D结构的LLZO骨架,且中间致密块体层同多孔3D结构的骨架层连接紧密。在3D结构的LLZO骨架中通过沉积一层ZnO等,可以很好的将熔融锂渗透到3D骨架结构中,并且这种结构的电池可以表现出在较高电流密度下的循环特性。但是这种酸处理的方法也存在一些问题,如酸刻蚀后3D结构的厚度不能精确控制,且根据目前来看,其厚度尺寸仅在50μm范围内,目前尚不清楚此种3D结构的层厚是否会对电池性能有较大的影响。此外,通过酸处理将LLZO块体整体浸泡,不仅会形成上下两侧的3D结构,也会对左右两侧的结构造成破坏,且极易对晶界进行刻蚀,在更高电流密度下,存在被锂枝晶穿透的风险。
鉴于此,我们提出一种全新3D结构的LLZO块体材料,通过添加造孔剂或粘结剂来实现3D结构骨架的形成,通过加压成型和后续热处理的方式最终来形成所述的3D结构LLZO块体材料。目前也有通过流延法制备具有3D结构骨架的三层LLZO块材。这种方法的优势是可以将中间层做到20μm左右,但其缺点是采用流延法不可避免的需要制备流延浆料,而这种浆料的制备需要采用较多的对人体有害的有机溶剂,而另一个关键的原因是采用流延法制备的中间层由于受制于工艺原因很难有较高的致密度,这可能会对后续全固态锂电池的性能有影响。
因此,本发明的一种电解质材料,所述陶瓷材料具有3D结构,从上至下依次包括骨架层、致密层和骨架层。
在进一步的实施例中,所述陶瓷材料的化学通式为Li7-3x-y+z A x La3Zr2-yB y O12+z/2;
式中,A为三价金属元素,B为五价金属元素,0<x≤0.4,0.4≤y≤0.8,0≤z≤1.4。
在进一步的实施例中,所述陶瓷材料的化学通式为Li7-3x-2w+z A x La3Zr2-wC w O12+z/2;
式中,A为三价金属元素,C为六价金属元素,0<x≤0.4,0.1≤w≤0.7,0≤z≤1.4。
以上两个式中,优选0.1≤x≤0.3,0.4≤y≤0.7,0.1≤w≤0.4,0.1≤z≤1,具有更高的锂离子电导率。
在进一步的实施例中,Li源为Li2CO3、LiOH、LiHCO3、CH3COOLi、CHOOLi、LiNO3、或其水合物中的至少一种;
La源为La2O3、La(OH)3、La2(SO4)3、乙酸镧、LaCl3、La(NO3)3、或其水合物中的至少一种;
Zr源为ZrO2、ZrCl4、ZrO(NO3)2、碱式碳酸锆、锆粉、二氢化锆、或其水合物中的至少一种。
在进一步的实施例中,所述A为Al或Ga;
其中,Al源为Al(OH)3、Al2O3、Al(PO3)3、Al(NO3)3、AlCl3、Al2(SO4)3、或其水合物中的至少一种;
Ga源为Ga2O3、GaCl3、Ga(NO3)3、Ga2(SO4)3、或其水合物中的至少一种。
在进一步的实施例中,B为Ta或Nb,其中,Ta/Nb源为Ta2O5/ Nb2O5、钽粉/铌粉、TaCl5/NbCl5、乙醇钽/乙醇铌、或其水合物中的至少一种。
在进一步的实施例中,C为W、Te,其中,W源为WO2、WO3、WCl6、钨粉、钨酸、或其水合物中的至少一种;
Te源为TeO2、碲粉、或其水合物中的至少一种。
制备如上所述的一种电解质材料的制备方法,具体包括以下步骤:
步骤一、将原材料按照合成组分所示化学式进行配比,得到混合物;
步骤二、将混合物装入混料设备中,加入弥散剂进行球磨或混合,达到混匀目的,完成后将混合物烘干;
步骤三、将烘干后的混合物放入加热设备中进行热处理,在700~950℃下热处理1~10h,得到预烧后LLZO粉体;优选的在750~900℃下热处理2~8h,更优选的在800~850℃下热处理4~6h,最优选的在825℃下热处理5h,
步骤四、将预烧后LLZO粉体进行破碎,并进行亚微米化处理;
步骤五、按照上层为3D结构骨架层、中间为致密层、下层为3D结构骨架层的顺序铺设粉层,压制成型为固体电解质块体,并对块体进行加热处理得到具有3D结构的LLZO体系陶瓷块体材料。
在进一步的实施例中,所述步骤四具体包括以下流程:用醇类作为弥散剂进行行星式球磨,粉体烘干后将其中一部分粉体添加粘结剂或造孔剂并混合均匀;混合有粘结剂或造孔剂的粉体,同时用于作为上层的3D结构骨架层和下层的3D结构骨架层;
粘结剂或造孔剂选用PVA、PMMA、淀粉、PVP、PEG、碳酸氢铵或尿素中的至少一种。
在进一步的实施例中,所述步骤五中的热处理采用一步处理或者两步处理;
当采用一步处理时,热处理的条件为:温度1100~1300 ℃下处理0.1~4h;优选的,1150~1250 ℃下处理1~3h;更为优先的1200 ℃下处理2h;
当采用两步处理时,热处理的条件为:第一步在温度1100~1300 ℃下处理0.1~1h,优选的,1150~1250 ℃下处理0.3~0.8h;更为优先的1200 ℃下处理0.5h;而后自然降温至第二步在1000~1200 ℃下处理0.1~8h,优选的,1050~1150 ℃下处理2~6h;更为优先的1100℃下处理4h;
一种电解质材料的制备方法制备出来的固体电解质材料在电池中的应用,位于上层的3D结构骨架层用于填充正极材料形成复合正极,位于下层的3D结构骨架层用则用于填充负极材料形成复合负极。
通过上述方法压制成型的固体电解质材料的结构如图1所示,包括上、中、下三层,其中,上层和下层的粉体中混合有粘结剂或造孔剂,来实现上层与下层的多孔3D骨架层,中间层则是通过粉体直接压制成型。
现有液态锂电池中无法使用金属锂作为负极,金属锂作为负极时会与电解液发生化学反应形成SEI(固体电解质界面)膜,但是金属锂负极在反复的充放电过程中,由于电流分布的不均匀及体积的膨胀,会引起SEI膜的反复破裂和形成,造成锂枝晶的产生和生长,一方面引起金属锂的损失,另一方面消耗电解液造成电池性能的衰减,在极端情况下甚至刺穿隔膜,引起正负极短路,造成安全事故。
全固态电池由于不含电解液,因此使得金属锂的使用成为可能。本专利中使用具有多孔3D骨架层的固体电解质制备全固态电池,当金属锂通过熔融的方式进入一侧多孔3D骨架中时,仍需要保持该侧顶部表面可见少量金属锂从而保证集流体侧电子和离子的传导。具备3D骨架结构的全固态锂电池可达以下效果:1、锂金属在充放电过程中会发生体积膨胀,而多孔3D骨架结构则给锂金属提供了一定的体积膨胀空间,同时一体化结构极大降低了充放电过程中中间层(电解质层)同下层(负极层)出现界面恶化的情况;2、多孔3D骨架的结构形式增加了充放电过程中锂离子迁移通道的面积,可以使得锂金属更为均匀的沉积,故而能够实现全固态锂金属电池在较高电流密度下的循环稳定性;3、上层(正极层)多孔3D骨架结构填充正极材料,尽管锂离子的迁移通过固-固颗粒之间传输通道实现,由于3D结构骨架使得锂离子迁移通道的面积增加,故而可以满足高电流密度下的离子迁移。
中层(电解质层)的粉末不使用粘结剂或造孔剂,从而确保电解质层的致密度。同时,需要尽可能的降低电解质层的厚度,保证锂离子的迁移更加容易。一般而言,中层(电解质层)的厚度控制在0.1~1mm之间。上、下3D骨架层的厚度控制在0.1~10mm之间,可根据实际情况进行机械减薄处理。
上、中、下层采用一体压制成型,避免了电池在充放电过程中由于各层体积变化不同造成应力不均,从而造成电池性能衰减。
实施例1
将Li2CO3、La2O3、ZrO2、Ta2O5按照Li7.04La3Zr1.4Ta0.6O12.32化学计量比配料,加入无水乙醇混合均匀后干燥处理。将干燥完成后的粉料热处理到950℃保温4h,冷却后湿磨条件下粉碎并干燥。干燥后的粉体部分加入质量浓度为6%的PVA溶液,添加量为粉体质量的30%,并充分研磨混合均匀。在φ18mm的磨具中先加入一层添加过PVA的粉体约0.8g,震实后再次添加未添加PVA的粉体约0.7g,震实后最后再添加加入PVA的粉体约0.8g,震实后在压机中压制成型为块体材料。将块体材料在700℃下保温2 h,随炉冷却后再次以1200℃保温1h于铂金坩埚中热处理,得到Li6.5La3Zr1.4Ta0.6O12.05组分的3D骨架结构的石榴石固体电解质材料。这种陶瓷材料两侧由于添加PVA的粉体故而表现出多孔结构,而中间层由于采用铂金坩埚烧结故而表现出致密结构。致密层厚度约为0.7mm,相对密度达到98%,两侧多孔层厚度也约0.8mm左右,相对密度只有75%。
实施例2
将LiOH·H2O、La(OH)3、ZrO2、Nb2O5按照Li6.7La3Zr1.5Ta0.5O12.1化学计量比配料,加入正丁醇混合均匀后干燥处理。将干燥完成后的粉料热处理到900℃保温6h,冷却后湿磨条件下粉碎并干燥。干燥后的粉体部分加入质量浓度为8%的PMMA溶液,添加量为粉体质量的40%,并充分研磨混合均匀。在φ20mm的磨具中先加入一层添加过PMMA的粉体约1g,震实后再次添加未添加PMMA的粉体约1g,震实后最后再添加加入PMMA的粉体约1g,震实后在压机中压制成型为块体材料。将块体材料在800℃下保温1 h,随炉冷却后再次以1225℃保温40min于铂金坩埚中热处理,得到Li6.7La3Zr1.5Ta0.5O12.1组分的3D骨架结构的石榴石固体电解质材料。这种陶瓷材料两侧由于添加PMMA的粉体故而表现出多孔结构,而中间层由于采用铂金坩埚烧结故而表现出致密结构。致密层厚度约为0.8mm,相对密度达到97%,两侧多孔层厚度也约0.7mm左右,相对密度只有70%。
实施例3
将LiOH·H2O、La2O3、Ga2O3、ZrO2按照Li7.45Ga0.25La3Zr2O12.6化学计量比配料,加入异丙醇混合均匀后干燥处理。将干燥完成后的粉料热处理到800℃保温2h,冷却后湿磨条件下粉碎并干燥。干燥后的粉体部分加入质量浓度为10%的PEG溶液,添加量为粉体质量的80%,并充分研磨混合均匀。在φ20mm的磨具中先加入一层添加过PEG的粉体约2g,震实后再次添加未添加PEG的粉体约1g,震实后最后再添加加入PEG的粉体约2g,震实后在压机中压制成型为块体材料。将块体材料在600℃下保温4h,随炉冷却后再次以1150℃保温5min而后迅速于铂金坩埚中自然冷却至1050℃保温2h进行热处理,得到Li6.7La3Zr1.5Ta0.5O12.1组分的3D骨架结构的石榴石固体电解质材料。这种陶瓷材料两侧由于添加PEG的粉体故而表现出多孔结构,而中间层由于采用铂金坩埚烧结故而表现出致密结构。致密层厚度约为1mm,相对密度达到98%,两侧多孔层厚度也约1.5mm左右,相对密度只有58%。
实施例4
将Li2CO3、La(OH)3、ZrO2、Ta2O5、Al2O3按照Li7Al0.1La3Zr1.5Ta0.5O12.4化学计量比配料,加入无水乙醇混合均匀后干燥处理。将干燥完成后的粉料热处理到900℃保温6h,冷却后湿磨条件下粉碎并干燥。干燥后的粉体部分加入质量浓度为15%的PVP溶液,添加量为粉体质量的20%,并充分研磨混合均匀。在φ18mm的磨具中先加入一层添加过PVP的粉体约1g,震实后再次添加未添加PVP的粉体约0.7g,震实后最后再添加加入PVP的粉体约1g,震实后在压机中压制成型为块体材料。将块体材料在600℃下保温4 h,随炉冷却后再次以1180℃保温2h于铂金坩埚中热处理,得到Li6.3Al0.1La3Zr1.5Ta0.5O12.05组分的3D骨架结构的石榴石固体电解质材料。这种陶瓷材料两侧由于添加PVP的粉体故而表现出多孔结构,而中间层由于采用铂金坩埚烧结故而表现出致密结构。致密层厚度约为0.7mm,相对密度达到98.5%,两侧多孔层厚度也约0.9mm左右,相对密度只有80%。
实施例5
将LiOH·H2O、La(OH)3、ZrO2、WO3按照Li6.9La3Zr1.75W0.25O12.2化学计量比配料,加入异丙醇混合均匀后干燥处理。将干燥完成后的粉料热处理到850℃保温6h,冷却后湿磨条件下粉碎并干燥。干燥后的粉体部分加入质量浓度为3%的PEG溶液,添加量为粉体质量的50%,并充分研磨混合均匀。在φ20mm的磨具中先加入一层添加过PEG的粉体约1g,震实后再次添加未添加PEG的粉体约0.8g,震实后最后再添加加入PEG的粉体约1g,震实后在压机中压制成型为块体材料。将块体材料在750℃下保温1 h,随炉冷却后再次以1200℃保温45min于铂金坩埚中热处理,得到Li6.6La3Zr1.75W0.25O12.05组分的3D骨架结构的石榴石固体电解质材料。这种陶瓷材料两侧由于添加PEG的粉体故而表现出多孔结构,而中间层由于采用铂金坩埚烧结故而表现出致密结构。致密层厚度约为0.7mm,相对密度达到96%,两侧多孔层厚度也约0.9mm左右,相对密度只有65%。
综上所述,本发明只需要成型磨具、加压和热处理工艺即可实现三层固体电解质的可控制备,比流延法制备所需的工艺要求简单很多,可行性高,即便是针对量产规模,此种工艺方法也具有较大的推广性,没有有机溶剂加入带来的工艺及安全风险。
通过添加粘结剂或造孔剂这种低成本、简单的工艺方法,可以实现全固态锂金属电池在较高电流密度下的稳定循环,为石榴石基全固态锂电池的制备奠定了基础。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (10)
1.一种电解质材料,其特征在于,所述电解质材料为陶瓷材料,所述陶瓷材料具有3D结构,从上至下依次包括骨架层、致密层和骨架层。
2.根据权利要求1所述的一种电解质材料,其特征在于,所述陶瓷材料的化学通式为Li7-3x-y+z A x La3Zr2-yB y O12+z/2;
式中,A为三价金属元素,B为五价金属元素,0<x≤0.4,0.4≤y≤0.8,0≤z≤1.4。
3.根据权利要求1所述的一种电解质材料,其特征在于,所述陶瓷材料的化学通式为Li7-3x-2w+z A x La3Zr2-wC w O12+z/2;
式中,A为三价金属元素,C为六价金属元素,0<x≤0.4,0.1≤w≤0.7,0≤z≤1.4。
4.根据权利要求1所述的一种电解质材料,其特征在于,Li源为Li2CO3、LiOH、LiHCO3、CH3COOLi、CHOOLi、LiNO3含Li物质或其水合物中的至少一种;
La源为La2O3、La(OH)3、La2(SO4)3、乙酸镧、LaCl3、La(NO3)3、或其水合物中的至少一种;
Zr源为ZrO2、ZrCl4、ZrO(NO3)2、碱式碳酸锆、锆粉、二氢化锆、或其水合物中的至少一种。
5.根据权利要求2或3任一项所述的一种电解质材料,其特征在于,所述A为Al或Ga;
其中,Al源为Al(OH)3、Al2O3、Al(PO3)3、Al(NO3)3、AlCl3、Al2(SO4)3、或其水合物中的至少一种;
Ga源为Ga2O3、GaCl3、Ga(NO3)3、Ga2(SO4)3、或其水合物中的至少一种。
6.根据权利要求2所述的一种电解质材料,其特征在于,B为Ta或Nb,其中,Ta/Nb源为Ta2O5/ Nb2O5、钽粉/铌粉、TaCl5/NbCl5、乙醇钽/乙醇铌、或其水合物中的至少一种。
7.根据权利要求3所述的一种电解质材料,其特征在于,C为W、Te,其中,W源为WO2、WO3、WCl6、钨粉、或其水合物中的至少一种;
Te源为TeO2、碲粉、或其水合物中的至少一种。
8.制备如权利要求2或3任意所述的一种电解质材料的制备方法,其特征在于,具体包括以下步骤:
步骤一、将原材料按照合成组分所示化学式进行配比,得到混合物;
步骤二、将混合物装入混料设备中,加入弥散剂进行球磨或混合,达到混匀目的,完成后将混合物烘干;
步骤三、将烘干后的混合物放入加热设备中进行热处理,在700~950℃下热处理1~10h,得到预烧后LLZO粉体;优选的在750~900℃下热处理2~8h,更优选的在800~850℃下热处理4~6h,最优选的在825℃下热处理5h,
步骤四、将预烧后LLZO粉体进行破碎,并进行亚微米化处理;
步骤五、按照上层为3D结构骨架层、中间为致密层、下层为3D结构骨架层的顺序铺设粉层,压制成型为固体电解质块体,并对块体进行加热处理得到具有3D结构的LLZO体系陶瓷块体材料。
9.根据权利要求8所述的一种电解质材料的制备方法,其特征在于,所述步骤四具体包括以下流程:用醇类作为弥散剂进行行星式球磨,粉体烘干后将其中一部分粉体添加粘结剂或造孔剂并混合均匀;混合有粘结剂或造孔剂的粉体,同时用于作为上层的3D结构骨架层和下层的3D结构骨架层;
粘结剂或造孔剂选用PVA、PMMA、淀粉、PVP、PEG、碳酸氢铵或尿素中的其中至少一种。
10.一种使用如权利要求8所述的一种电解质材料的制备方法制备出来的固体电解质材料在电池中的应用,位于上层的3D结构骨架层用于填充正极材料形成复合正极,位于下层的3D结构骨架层用则用于填充负极材料形成复合负极。
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