CN113937275A - 一种掺杂改性硅酸亚铁锂碳复合材料的固相合成制备方法 - Google Patents
一种掺杂改性硅酸亚铁锂碳复合材料的固相合成制备方法 Download PDFInfo
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 11
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
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- 238000002844 melting Methods 0.000 claims abstract description 9
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical class [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 2
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- 239000000126 substance Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000010406 cathode material Substances 0.000 description 8
- 229910009731 Li2FeSiO4 Inorganic materials 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 239000002033 PVDF binder Substances 0.000 description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
本发明属于锂离子电池及其制造的技术领域,提供一种采用固相合成法制备锂离子电池正极材料掺杂改性硅酸亚铁锂碳复合材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C的方法,该方法将锂源、铁源、锰源、硅源和钒源材料混合后在1180~1280℃的温度下熔化得到非晶化合物,再添加碳源材料进行研磨,对研磨后的粉体材料进行循环热处理,获得含有总体积10~30%的非晶相的复合材料。非晶相可以有效提高锂离子在硅酸盐材料中的扩散能力,提高了材料的比能量。
Description
技术领域
本发明属于锂离子电池及其制造的技术领域,具体为一种采用固相合成法制备锂离子电池正极材料掺杂改性硅酸亚铁锂碳复合材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C的方法,提高了锂离子在硅酸盐材料中的扩散能力。
背景技术
聚阴离子型正极材料硅酸亚铁锂(Li2FeSiO4)具有高理论容量330mAh/g,原料资源储藏丰富,工作电压稳定,Si-O键具有出色的热稳定性以及材料的环保、低成本等优点,在高能量锂电池中成为引人注目的正极材料之一。然而Li2FeSiO4材料本身的导电性较差,离子导电率低等缺点,因此提高材料导电率和锂离子的扩散系数成为研究的重点。
非晶相硅酸盐可以作为锂离子导体,提高锂离子在硅酸盐中的扩散能力。专利CN200910108495.9对硅酸亚铁锂进行了掺杂过渡金属元素的技术处理,过渡金属元素包括钴、锰、镍、钒或钛,未提及加入钒是作为结晶抑制剂,并以获得非晶相材料为目的。专利CN201410012564.7采用溶胶凝胶法,以铁粉为铁源,纳米二氧化硅为模板,原位生成碳包覆的硅酸亚铁锂正极材料,制备过程的前驱体低温下实现预分解,形成成分均匀的非晶复合物,最后经高温烧结形成纳米尺度的硅酸亚铁锂,结晶度高,可见该专利在最终产品中并没有保留非晶相,保留非晶相也不是该专利的目的。其他有关硅酸亚铁锂及其改性材料利用非晶相以增强锂离子在材料中的扩散性的技术方案尚未见到公开报道。
发明内容
(一)要解决的技术问题
本发明提供一种采用固相合成法制备锂离子电池正极材料掺杂改性硅酸亚铁锂碳复合材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C的方法,解决的技术问题为制取具有部分非晶相的改性硅酸亚铁锂碳复合材料,提高锂离子在硅酸盐材料中的扩散能力,提高其电化学性能。
(二)技术方案
本发明的技术方案是:
一种锂离子电池聚阴离子型正极材料掺杂改性硅酸亚铁锂碳复合材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C的固相合成制备方法,其制备过程包括以下步骤:
步骤1、将适量的草酸亚铁和乙酸锰以及对应量的硅酸锂、二氧化硅及相应比例的V2O5粉末混合,加热至1180~1280℃熔化,再冷却至室温,形成非晶化合物;原料的配比应保证元素摩尔比为Li:Fe:Mn:Si:V=2:0.5:0.5:(0.55~0.70):0.025;其中锂硅元素摩尔比优选为Li:Si=2:0.6,熔化温度优选为1180℃;
步骤2、将非晶化合物并添加碳源进行研磨;其中,碳源中的碳元素含量为非晶化合物总重的的1.5~3wt%;
步骤3、将球磨后的粉体材料在保护气体氛围中进行循环热处理,即加热到温度600~700℃,保持55-65分钟,冷却到室温,进行5-10次循环,最后得到含有总体积10~30%的非晶相的复合材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C。
优选的,
步骤1中,所述硅酸锂具体为Li4SiO4;
步骤2中,所述碳源为聚甲基丙烯酸甲酯、蔗糖、葡萄糖中的一种或几种;
步骤2中,所述研磨方式为球磨,速度500r/min,时间12h;
步骤3中,所述保护气体为氮气、氩气中的一种。
当锂硅元素摩尔比Li:Si=2:(0.55~0.7)的范围,以及熔化温度1180~1280℃的范围时,混合物熔化后在空气中冷却时可以实现完全非晶化,其中最佳锂硅元素摩尔比为Li:Si=2:0.6,最佳熔化温度为1180℃。非晶相硅酸盐是锂离子导体,可作为锂离子的传输通道,提高锂离子在硅酸盐材料中的扩散能力。五氧化二钒对非晶化合物的结晶效率有一定影响,可作为结晶抑制剂改善硅酸盐的结晶结构和相组成。
正极材料晶体中Mn离子进入,取代部分Fe离子,改变了正极材料的晶体结构,或增加了锂离子的嵌入空间,或降低了锂离子跃迁能级,可以提高正极材料的比能量。
所述碳源的碳元素含量低于非晶化合物总重的1.5wt%时,会导致材料的电导率较低;但含量超过3wt%时也会降低电池的比能量,1.5~3wt%是个较佳的范围。
高能球磨有助于将碳源聚合到粉末颗粒上,形成均匀的图层,在球磨过程中也可以初步获得非晶相和晶相。
随后进行循环热处理,可以获得稳定量的纳米晶相和非晶相。当循环次数为5至10次时,非晶相的比例为粉末总体积的10至30%。通过非晶相和结晶相的这种比例,可以实现电池的高比能量。此外,在600℃以上的循环温度下,发生所需的晶相生长,其尺寸超过200nm。在<600℃的温度下,热处理时间会显着增加,达到10天以上。
(三)有益效果
本发明相对于现有技术,具有以下有益效果:
1、通过选择特定范围的锂硅元素摩尔比和熔化温度,实现材料的完全非晶化;添加五氧化二钒可以作为结晶抑制剂,有助于完全非晶化的稳定获得,有助于后续烧结完成后继续保持总体积10~30%的非晶相,有利于提高锂离子在材料中的扩散能力;2、采用循环热处理,可以获得稳定量的纳米晶相和非晶相,总体积10~30%的非晶相可以实现电池的高比能量。
附图说明
图1是实施例1制备的正极材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C的XRD图谱;
图2是实施例1制备的正极材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C的SEM图;
图3是实施例1制备的正极材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C在0.05C倍率下的充放电曲线;
图4是实施例1制备的正极材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C与其他Li2FeSiO4基材料的电化学性能对比图。
具体实施方式
为更好地说明本发明,便于理解本发明的技术方案,本发明的典型但非限制性的实施例如下:
实施例1
(1)将3.6g草酸亚铁、4.33g乙酸锰、4.86g硅酸锂、0.5g二氧化硅和0.11gV2O5粉末混合;
(2)将上述混合粉体材料加热至1180±5℃熔化,±5℃为测温误差范围,再冷却至室温,形成非晶化合物;
(3)向非晶化合物中添加碳源进行球磨,球磨速度500r/min,时间12h;
(4)将球磨后的粉体材料在氮气氛围中进行循环热处理,即加热到温度700℃,保持55分钟,冷却到室温,进行10次循环,最后得到正极材料Li2Fe0.5Mn0.5Si0.975V0.025O4/C。
对实施例1制备的正极材料进行物理表征测试,XRD图谱(图1)表明所合成的正极材料属于700℃-P21/n晶相,出现少量Li2SiO3衍射峰。SEM图(图2)表明正极材料的粒径<3μm。
对实施例1制备的正极材料按照Li2Fe0.5Mn0.5Si0.975V0.025O4/C:Super P Li:PVDF以8:1:1(by mass)比例研磨混料,氮甲基吡咯烷酮(NMP)溶解PVDF(10%溶液),经搅拌调浆、制膜、压片、冲片、真空烘干、称重,制备好正极电极片,在手套箱中组装扣式CR2032型半电池,搁置后进行充放电测试。正极材料在0.05C倍率下的充放电曲线(图3)表明首圈充电363mAh/g,首圈放电182mAh/g;第2圈充电262mAh/g,放电191mAh/g,充电曲线电压平台出现在4.0V以上,且第二圈电压平台降低比Li2FeSiO4要小。
实施例1制备的正极材料与基材Li2FeSiO4、纳米化的Li2FeSiO4,碳复合Li2FeSiO4/C、掺锰改性Li2Fe0.5Mn0.5SiO4/C的电化学性能比较(图4)表明,充电容量从130mAh/g逐步增加到335mAh/g,放电容量由100mAh/g增加到193mAh/g。
Claims (6)
1.一种掺杂改性硅酸亚铁锂碳复合材料的固相合成制备方法,其特征在于,所述掺杂改性硅酸亚铁锂碳复合材料的化学式为Li2Fe0.5Mn0.5Si0.975V0.025O4/C,其制备过程包括以下步骤:
步骤1、将适量的草酸亚铁和乙酸锰以及对应量的硅酸锂、二氧化硅及相应比例的V2O5粉末混合,加热熔化,再冷却至室温,形成非晶化合物;
步骤2、将非晶化合物并添加碳源进行研磨;
步骤3、将球磨后的粉体材料在保护气体氛围中进行循环热处理,得到掺杂Mn、V元素的改性硅酸亚铁锂碳复合材料;
上述制备过程中,
步骤1中的原料的配比应保证元素摩尔比为Li:Fe:Mn:Si:V=2:0.5:0.5:(0.55~0.70):0.025;
步骤1中的熔化温度为1180~1280℃;
步骤2中的碳源中的碳元素含量为非晶化合物总重的1.5~3wt%。
2.根据权利要求1所述的制备方法,其特征在于,
步骤3中,循环热处理过程为加热到温度600~700℃,保持55-65分钟,冷却到室温,进行5-10次循环。
3.根据权利要求1所述的制备方法,其特征在于,
步骤1中,所述硅酸锂具体为Li4SiO4;
步骤2中,所述碳源为聚甲基丙烯酸甲酯、蔗糖、葡萄糖中的一种或几种;
步骤3中,所述保护气体为氮气、氩气中的一种。
4.根据权利要求1所述的制备方法,其特征在于,
步骤2中,所述研磨方式为球磨,速度500r/min,时间12h。
5.根据权利要求1所述的制备方法,其特征在于,
步骤1中,所述原料配比应保证元素摩尔比Li:Si=2:0.6。
6.根据权利要求1所述的制备方法,其特征在于,
步骤1中,所述熔化温度为1180℃。
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