Iolanda S. Klein,* Zuofeng Zhao, Stephen K. Davidowski, Jeffery L. Yarger, and C. Austen Angell

Transcription

1 Communication 固体 Solid Electrolytes 电解质 A New 新型 Version of the 锂 Lithium 离子导电 Ion Conducting 塑料 Plastic Crystal 固体 Solid 电解质 Electrolyte Iolanda S. Klein,* Zuofeng Zhao, Stephen K. Davidowski, Jeffery L. Yarger, and C. Austen Angell Excluding aqueous 水溶液溶液 solutions, the 便携式 Portable 电子 electronic devices 设备 are 主要是 predominantly 供电 powered by 锂 lithium 离子 ion highest 最高 ambient 环境温度 temperature conductivities of 锂 lithium 含 containing 材料 materials 已 have 电导率电池 batteries in which the 电解质 electrolyte is a 液体 liquid or 或 gel 凝胶 of lithium 锂 salts 盐 dissolved 溶解 in 分子 molecular 溶剂 solvents. There 有 have been 许多 many 尝试 attempts to 替代 replace the flammable been 发现 found, not 不 in 液体 liquid, but 而 in 玻璃 glassy, mixed 混合玻璃 glass-crystal 晶体 and 和 crystal 晶体 phases. 相 The 液体 liquid component 组分 of the electrolyte by 替代 alternative 碱 alkali metal 金属 transporting 介质 media, partly 部分再结晶 recrystallized thiophosphate 玻璃 glass 如 such as 超离子 superionic 晶体 crystals, 碱 alkali-conducting 玻璃 glassy 固体 solids, 离子 ionic 液体 liquids, saltin-molecular 分子 plastic 塑料晶体 crystal 溶剂 solvent, and 和 salt-in-ionic 盐离子 plastic 塑料 crystal 晶体 solvents. 溶剂现 exhibited an 环境 ambient 温度 temperature 导电 con- reported 报道 by Tatsumisago and co-workers [3] 之外 Except for the first 两个 two of the above, which 具有 have 其 their 自身 own 问题 problems, 所有 all the ductivity of a remarkable 17 ms cm 1, significantly higher than the 最高 highest 报道 reported above have 具有 the disadvantage 缺点 that the 碱 alkali 阳离子 cation is the 最小 least 移动 mobile of the 离子 ionic species 物质 due to 其 its 高 high 电荷 charge/radius 半径比 ratio. 这里 Here, some 一些新 new, silylsulfatebased are 介绍 introduced. 成员 Members of the 类 class of 锂 lithium 离子导体 ion conductor in which in 非水 nonaqueous 电解质 electrolyte 溶液 solutions, and that has 现在 now been 超过 exceeded by a chlorinecontaining 变体 variant of the Kamaya et al. thiophosphogermanate 超离子 superionic 晶体 crystal [4] the 碱 alkali ion 离子 is the only 唯一 cationic 阳离子 species 物质 present, 存在 and 和 the salt 盐本身 itself is a plastic 塑料晶体 crystal, a solid 固体 in which the anion 阴离子 centers of mass 质 are 有序 ordered, but 但 the anion 阴离子 that exhibits 表现出 σ 25 C = 25 ms cm 1. [5] 部分 Part 取向 orientations are 无序 disordered 和 and 动态 dynamic (best 最好例子 example NaCB 9 H 10, see 见 text). of the 成功 success of 这些 these 固体 solid 电解质 electrolytes is It is shown 显示 that 取决 depending on the 性质 nature of the 阴离子 anion, the 电导率 conductivity 可以 may due to the fact that the 碱 alkali 阳离子 cation is 现在 now, not 不不仅 only the 最 most 移动 mobile 离子 ion, 而 but 通常 usually be within a 倍 factor of two 两 of the 标准 standard 液体 liquid 碳酸盐 carbonate 电解质 electrolyte. The 柔软 soft, the 不仅 only 移动 mobile 离子 ion. 然而 However, as 刚性 rigid spreadable 电解质 electrolyte, impregnated 浸渍 in Celgard separators, supports 支持真正 truly materials, 材料 they 它们 tend to be 机械 mechanically reversible 可逆 Li insertion 插入 into the LiCoO 2 cathode. 阴极 fragile and 和 are 易于 prone to 遇到 encounter junction 问题 problems with 阳极 anode 和 and 阴极 cathode materials. 材料优异 Excellent cell 电池 performance 性能 has The 功率 power that 可以 can be 提取 extracted from an 电化学 electrochemical 装置 device 尽管如此 nonetheless been 报道 reported. [5] of the 电池 battery 类型 type depends 取决很大程度 largely on the 速率 rate at which 正 positive An alternative 另一种 approach 方法 that avoids 避免 the liquid 液态 state 态 is to 溶解 dissolve 盐 salts in plastic 塑料晶 crystal phases. 相两种 Two 类型 types of plastic 塑料晶体 crystal 离子 ionic 电荷 charge 传输 transport (compensating 补偿 the 外部 external 流动 flow of 电子 electrons) 可以 can 恢复 restore the 中性 neutral 状态 state of the 装置 device. Here, 这里 we 我们集中 focus solvents 溶剂 have 有 been 研究 explored: (i) 分子 molecular 溶剂 solvent [6,7] (succinonitrile (SSN) in which a 盐 salt 如 like LiN(Tf) 2 is 溶解 dissolved) 和 and 注意力 attention on the 移动 mobility of lithium 锂 ions 离子 in condensed 物质 matter 因为 since the 锂 lithium 电池 battery has so 迄今为止 far 占主导地位 predominated in the 便携式 portable energy 能源市场 marketplace. 虽然 While the highest 最高 ambient 环境温度 tempera- are 溶解 dissolved, of which many 许多 variants 变体 [8 10] 有 have been 使用 employed. (ii) organic 有机阳离子 cation salts 盐 in which 盐 salts like 如 LiBF 4 和 and LiN(Tf) 2 ture 锂 lithium 离子 ion 电导率 conductivity in condensed 凝聚 phases 相 is found 发现 in 虽然 Although it was not 没有提到 mentioned in the 最初 initial 出版物 publication, [6] the 水溶液 aqueous 溶液 solutions of 中等 moderate 浓度 concentration, [1] 水溶液 aqueous 溶液 solutions of 这些 these 浓度 concentrations 不能 cannot be used 用 in 高 high-voltage in the ability 能力 of the 分子 molecular solvent 溶剂 (or 或分子 molecular ions), 离子 to success 成功 of the 塑料 plastic 晶体 crystal 状态 state as a 溶剂 solvent 在 lies 主要 primarily 设备 devices 因为 because of the facile 容易 electrochemical 电化学分解 decomposition of reorient on 短 short 时间 time scales (t reor 0.1 ns in the 情况 case of SSN [11] ) 水 water. 该 This 问题 problem can 可以 be overcome 克服 in certain 某些 ultraconcentrated (liquid 液体水合物 hydrate) 电解质 electrolytes, but 但 only 仅 at the 代价 expense of enjoy high 高迁移率 mobility. 虽然 While each 每个 case 案例 has been 认为 considered 成功 suc- thus 因此提供 providing a 高 high entropy medium 介质 within which the 离子 ions the 高 high 导电性 conductivity. [2] cessful, the disadvantage 缺点 of each 每个 is that the Li + 物种 species 被证明 proves to be the least 移动 mobile 物种 species. 这 This is 因为 because, due to its 其高 high 电荷 charge 半径 radius 比 ratio, the Li 阳离子 cation 占主导地位 dominates 竞争 competition for 配体 ligands 并 and digs 自身 itself a 空穴 hole in the 相同 same 方式 way as 其 it does in a Dr. I. S. Klein, Dr. Z.-F. Zhao, Dr. S. K. Davidowski, Prof. J. L. Yarger, Prof. C. A. Angell 典型 typical nonaqueous 非水分子 molecular 液体 liquid 电解质 electrolyte. A consequence 结果学院 School of Molecular 分子 Sciences 科学 is 低 low 迁移率 mobility of the 电活性 electroactive 物质 species 相对 relative to 其他 others, 亚利桑那州 Arizona State 大学 University 并 and consequent 极化 polarization problems 问题 during 操作 operation at high 高 Tempe, AZ , USA 电流 currents. 邮件 iolandask@gmail.com It 其 is against 这种 this 背景 backdrop that 我们 we have 寻求 sought to 开发 develop an The ORCID identification number(s) for the 作者 author(s) of 本 this 本文 article 改进 improved 型 type of 环境 ambient temperature 温度 plastic 塑料 crystal 晶体 ion 离子导体 conductor, one 一种 in which the only 唯一 mobile 移动 species 物种 is the 碱 alkali 阳离子 cation 可以 can be found 找到 under DOI: /aenm so that (as in 超离子 superionic 玻璃 glasses 和 and 晶体 crystals) the 导电性 conductivity (1 of 7)

2 is unicationic. For 这 this to be 可能 possible it is necessary that the second 第二 nearest 近邻 neighbor of the alkali 碱阳离子 cation is a high 高电荷 charge (+3 and 和更高 higher) Lewis 路易斯 acid 酸物质 species, as in the 超离子 superionic crystal 晶体 and 和玻璃 glass 情况 cases, 和 and in 特别 particular is 不 not 第二 a second 弱 weak-field 场 cation 阳离子 as in 许多 many 情况 cases under 研究 study. To 保持 maintain the 塑性 plastic condition, 条件 this 这种 anionic 阴离子 structure 结构 must 必须 be simple 简单 in shape 形状并 and without 任何 any 网络 network 连接 connectivity. There are 许多 many 离子 ionic 晶体 crystals that 满足 satisfy the above requirements 并 and 成为 become 超离子 superionic 固 solid-state 态导体 conductors at 某些 some 要求 temperature 温度 in 其 their 稳定 stability 范围 range, 但 but very 少数 few that 超过 exceed 1 ms cm 1 at the generally 通常 desired 所需应用 applications 温度 temperature of 25 C. For 例如 instance, LiBH 4, in which the anion 阴离子 has been identified by neutron 中子散射 scattering 研究 studies as 具有 having a reorientation 时间 time 鉴定 less 小 than s [12] 表现出 exhibits a 高 high 导电 conductivity (10 3 S cm 1 ) 但 but 仅 only above its 其转变 transition to a 高 high-temperature 温度相位 phase at about 115 C. By extrapolation, 外推 the 电导率 conductivity would only 仅 be 10 4 S cm 1 at ambient 环境 if the reverse 反向 transition 转变 was suppressed. 被抑制 The 电导率 conductivity of 结晶 crystalline LiAlCl 4, in which anion 阴离子 rotation 旋转 is 预期 expected, is moderately 适度 high 高 at 25 C, viz., 即 10 6 S cm 1. [13] Li 2 SO 4 is famous for 其 its 高 high 导电性 conductivity behavior 性能 due, 可以说 arguably, to 耦合 coupling of 硫酸 sulfate 阴离子 anion 旋转 rotation with Li 扩散 diffusion [14 16] 但 but only 仅 above 575 C. An outstanding 突出例外 exception is the most 最 recent 最新 member 成员 of a 类 class of 碱 alkali closo-borates. 硼酸盐 [17] The 钠 sodium 盐 salt of the monovalent 阴离子 anion [CB 9 H 10 ] has exhibited 表现出 a remarkable 25 C 电导率 conductivity of 30 ms cm 1 by 过冷 supercooling through its 相 phase 相变 transition at 47 C. [17] Refs. [17,18] provide 提供 ample 充分证据 evidence of 快速 fast 旋转 rotation of the 碳 carbon-containing 含和 and 碳 carbon-free 硼 boron 笼 cage 分子 molecular anions 阴离子 above their 其有序 order disorder 无序相 phase transitions. 另一种 Another 真正 truly 超离子 superionic 软 soft 固 solid 相 phase that evidently has 独特 uniquely 碱 alkali 阳离子 cationic mobility 迁移率 is the 情况 case of NaAl 2 Br 7, 观察到 observed incidentally 偶然 to the study 研究 of a 二元 binary 无机 inorganic 离子 ionic 液体 liquid. [19] The 圆柱形 cylindrical 阴离子 anion 盐 salt NaAl 2 Br 7 has a 高 high 焓 enthalpy 一 first-order 固 solid-state 态跃迁 transition at 60 C to a 塑性 plastic 相 phase with 电导率 conductivity of 10 ms cm 1. 该 This 值 value is within 10% of the 液态 liquid-state 态导电 conductivity 观察到 observed on 熔化 melting at 120 C, and 并 extrapolates to 3 ms cm I at 25 C. The 关系 relation H trans / H fus > 5, satisfies 满足 the Timmermans 标准 criterion for rotator phases. 相 There are 可能 likely to be others. 其他人 Here, 这里 we 我们描述 describe a 新 new 系列 series of bulbous 阴离子 anion 锂 lithium 盐 salts, with inoxidizable, weakly 弱 coordinating, 配位 singly 单 charged, 电荷 complex 复杂 sulfate 硫酸盐 moieties 部分 as the 负 negative charge 电荷 bearers. 其 These are 柔软 soft, waxy, sometimes 有时 gel-like 凝胶 solids 固体 with high 高度无序 disorder by X-ray 射线衍射 diffraction, whose appearance, 外观 superionic 超离子 conductivity, 导电性 and 和不寻常 unusual 性质 properties strongly 强烈 suggest 表明 they 它们 are also 也 rotator phases. 相 There are 各种 various 优点 advantages of rotator 相 phase 塑料 plastic 晶体 crystals over 玻璃 glasses. 首先 First, the 塑料 plastic crystals 晶体 are 柔韧 pliable, 减少 reducing the 问题 problem of 建立 establishing 和 and 保持 maintaining 良好 good 接触 contact with electrodes 电极 in the face of 体积 volume 变化 changes. A 第二 second 潜在 potential advantage 优势 is not 不 so 明显 obvious. 玻璃 Glasses only 仅 retain 其 their 形状 shape up to the 玻璃 glass 转变 transition 温度 temperature, T g, where the 剪切 shear modulus 模量衰减 decays to 零 zero on the 100 s 时间 time 尺度 scale. 塑料 Plastic 晶体 crystals, on the 另一 other 方面 hand, 也 also 表现 exhibit the 玻璃 glass 转变 transition [20] where the 取向 orientational order 顺序 becomes arrested, 阻止 but, 但 in contrast 相比 to glasses, 玻璃它们 they retain 它们 their solidity 有限 (finite 剪切 shear 模量 modulus) up to far 更高 higher 温度 temperatures. In 原则 principle, this 这 opens the 大门 door to higher 更高固 solid-state 态电导率 conductivities than 有 have been 获得 attained with superionic 超离子玻璃 glasses, though 尽管 this 这 will only 只有 be 实现 realized for 情况 cases of 等效 equivalent superionicity, as 定义 defined at T g. At 这个 this time, 我们 we have 具有 no 没有数据 data in the (experimentally 实验 challenging) 具有挑战性 range 范围 near 附近 T g, to address 解决 this 这个个问题 question. 塑料 Plastic 晶体 crystals are 通常 usually 特征 characterized by the 存在 presence of 不对称 asymmetric 颗粒 particles of globular 球状 or 或 short 短 tube-like 管 character, 特征 of which the succinonitrile 分子 molecule (CNCH 2 CH 2 CN) is a 很好 good example. 例子 In succinonitrile at ambient 环境温度 temperature, the reorientational relaxation 弛豫 time 时间 determined 确定 by 13 C NMR, is reported 报道 to be 50 ps, [21] a 液体 liquid-like 值 value, which helps 有助于 account 解释 for the finding that the 25 C 电导率 conductivity of LiTFSI 溶解 dissolved in succinonitrile is an 令人印象深刻 impressive 10 3 S cm 1. [6] Of course, the most 最 direct 直接 measure 测量 of reorientation 时间 times in 偶极 dipolar 分子 molecular 系统 systems is made by 介电 dielectric 谱 spectroscopy: 数据 data for succinonitrile are available over some ten 十个 orders of magnitude. 个数量级 [20] We 我们最近 recently 报道 reported the 发现 discovery of 软 soft 固体 solid 酸 acids of record-breaking 破坏 ambient 环境温度 temperature 电导率 conductivities [22] and the present 目前应用 application to 碱 alkali metal 金属 conducting 导电 solids 固体 is a natural 自然 extension 延伸 of that 工作 work. Indeed, in ref. [22], the formation 形成 of the lithium 锂盐 salts was 被用 invoked as a means 手段 of 阻止 arresting the 反应 reaction that was 形成 forming the 塑性 plastic 相 phase 氢 hydrogen 硫酸 sulfates for 那些 those cases 情况 in which the structure 结构 would otherwise 否则继续 continue to change 变化 with time. 时间 The state 状态 of the structure 结构 arrested could 可以 then 然后 be 确定 determined by 固 solid-state 状态 29 Si NMR. Accordingly, the lithium 锂离子导体 ion conductors of the present 本 report 报告 were produced as 软 soft 可变形 deformable 固体 solids by the 固体 solid-state 态 neutralization of mono 氢 hydrogen 硫酸 sulfate 固体 solid 酸 acids of SiX 3, using 中和 anhydrous 无水锂 lithium amide, 根据 according to the 以下 following equation SiX3SOH 4 (s) + LiNH2(s) SiX3SOLi 4 (s) + NH3(g) (1) where the 硅 silicon 配体 ligands X, can 可以 be as many as there are polyphenylated silane 硅烷前体 precursors (Si(ph) n X (4 n) ) available 可用 for selective reaction 反应 with sulfuric 硫酸 acid. When n = 1, a monoprotic 酸 acid 选择性 is obtained due to the 有利 favorable leaving 动力学 kinetics of the 苯基 phenyl 基 group in the 酸 acid-producing reaction 反应 (Equation (2)). This 这 was 证实 confirmed by 1 H 和 and 29 Si NMR spectroscopy 光谱 [22] Si(ph) nx(4 n) + H2SO4 SiX (4 n) (SO4H) n + nc6h6 (2) In 我们 our 目前 present 情况 case, 我们具有 we have 限制 restricted 活性 activity to 反应 reactions with trimethoxy-, triethoxy-, and 和三甲基 trimethyl-phenyl 苯基硅烷 silanes, in order to obtain 获得 the 单 singly lithiated 锂化 lithium 锂盐 salts of trimethoxy-, triethoxy-, and 和 trimethyl 三甲基 silyl 甲硅烷基氢 hydrogen sulfate. 硫酸 The 优点 advantage of using the phenylated 前体 precursors is that the 苯基 phenyl 配体 ligand is 更 much 更 more 容易 easily displaced by protonation 质子化 than the 其他 other 配体 ligands with the 结果 result that a 纯 pure (trimethyl) 三甲基或 or 接近 nearly 纯 pure (trialkoxy) product 产物 can 可以 be obtained (by decantation of the 产物 product 苯 benzene, followed 然后 by additional 额外 drying). 干燥 In the 情况 case of the 三甲基 trimethyl 化合物 compound, the simple 简单 nature 性质 of the 产物 product was 证实 confirmed by the 存在 presence of a 单 single 尖锐 sharp 29 Si 共振 resonance in the 前体 precursor 酸 acid 相 phase, which was a 液体 liquid. [22] In the 其他 other cases, 情况 some 一些 residual 残留 phenyl 苯基 groups 基 were implied 暗示 by the 存在 presence of 两个 two 29 Si resonances 共振 in the 前体 precursor 酸 acid 光谱 spectra [22] 和 and some 一些醇 alcohol in the 反应 reaction products. 产物 In the 早期 early 阶段 stages of the 研究 investigation, 我们尝试 we attempted to make 使 rotator 阶段 phases with 氯 chlorine 配体 ligands, using SiCl 4 starting 料 material, 但 but found 发现 that the 单一 single stable 稳定 product 产物 of the reaction with H 2 SO 4 was the 已知 known [23,24] 完全 fully 氢 hydrogen 硫酸化 sulfated 反应化合物 compound Si(SO 4 H) 4. 这 This is 也 also a 塑料 plastic 晶体 crystal with a 高 high proton 质子传导性 conductivity. [22] On LiNH 2 中和 neutralization, it 它 yields a (2 of 7)

3 软 soft 固体 solid 锂 lithium 盐 salt Li 4 Si(SO 4 ) 4 that also has an 令人印象深刻 impressively high 高导电性 conductivity, especially 特别是 for a salt 盐 with a tetravalent 四价 anion. 阴离子 Whether 是否 the 球状 globular anion 阴离子 can 可以 rotate 旋转 freely 自由 or not must 必须 be decided 决定 by 进一步 further 研究 studies, possibly 可能 using NMR study 研究 of a selenate 硒酸盐类似物 analog. 不幸 Unfortunately, 介电 dielectric 谱 spectroscopy is no 不 longer 可行 viable when the 系统 system has a 高 high 导电 conductivity. Specific 比电导率 conductivity 数据 data on Li 4 Si(SO 4 ) 4 (Li4), Li(CH 3 ) 3 SiO- SO 3 三甲基 (trimethyl), Li(OCH 3 ) 3 SiO-SO 3 (trimethoxy), 和 and Li(OCH 2 CH 3 ) 3 SiO-SO 3 (triethoxy) were 获得 obtained using a twin Pt 电极 electrode 浸 dip-type cell 电池 in conjunction with a PARSTAT VMP2 using a 10 mv 极化 polarization 和 and 频率 frequency 范围 range of 10 Hz to 200 khz. 其他 Other 细节 details are found in ref. [22]. The 浸 dip-type 型 cell 电池 is 令人满意 satisfactory for these 这些软 soft 固体 solids 因为 since the 测试 test 材料 material 可以 can relax around the penetrating 穿透 platinum 铂 electrodes 电极并 and make 良好 good 接触 contact so long as the plastic 塑性 phase 相 is retained. 保留 In Figure 图 1, the findings 发现 for the above 化合物 compounds are 比较 compared with the 最佳 best of the forerunners among 超离子 superionic 晶体 crystalline, glassy-crystal, 玻璃晶体 rotator phase 相 alkali 碱 salts 盐 and 和 standard 标准分子 molecular 溶剂 solvent + LiPF 6 cases. A single, 单一 ambient 环境温度 temperature, 数据 datum is 包括 included for the less 导电 conductive 三 tri-ethoxy compound. 化合物 In 讨论 discussing 我们的结果 our results, we 我们将 will henceforth use 使用 the 名称 designations 三甲基 trimethyl, trimethoxy, and 和 Li4, for these 这些 compounds, 化合物 for sake of simplicity 简单 and 和经济 economy. The 电导率 conductivity of 三甲基 trimethyl is seen to be within a 倍 factor of 2 of that of the 标准 standard 碳酸盐 carbonate 电解质 electrolyte at 50 C, and 并 the 数据 data 点 points fall on 顶部 top of the 图 plot for the Li Si 1.35 P 1.65 S 12 superionic 超离子晶体 crystal. In making 使 the comparison 比较 with the standard 标准 电解质 electrolyte it 此 must 必须 be 记住 remembered that 我们的材料 our material, 如 like the 超离子 superionic crystal, 晶体 is a 单 single 离子 ion (Li + ) 导体 conductor, and 与因此 consequently is free of 极化 polarization problems, 问题 even under 高 high current 电流流 flow. Further 优点 advantages of the 新 new 材料 materials 将 will be seen 看到 below where we 我们检查 examine the 阴极 cathode redox 氧化还原动力学 kinetics in a cathode 阴极半 half 电池 cell (button 纽扣型 type). Data 数据 extend 延伸 to well below 0 C in the case 情况 of the Li4 material 但 but 我们 we have had trouble 延伸 extending 测量 measurements on 材料 trimethyl 三甲基 to 低 low temperatures in consequence of 它 its strong tendency to undergo a 相 phase change to a 较低 lower-conducting 导电 nonplastic 相 phase. Below, we 我们提供 provide preliminary 初步 results 结果 on a strategy 该策略 to stabilize 稳定 the 塑料 plastic phase 相 thermodynamically 热力学 by a method 方法已经 already 证实 proven for 塑料 plastic 分子 molecular 晶体 crystals. 我们将 We will be reporting 报告 further 进一步低 low temperature 数据 data for these 这些新 new 材料 materials in a separate 论文 paper in which 我们引入 we introduce a 新 new 技术 technique for examining 检查 the 电导率 conductivities of 样品 samples that are 永久 permanently sealed 密封 into a 玻璃 glass NMR 管 tube to permit 联合 joint NMR-conductivity studies 研究 at 我们的休闲 our leisure. [26] 结果 Findings 可以 can 已经 already be 预期 antici- 电导率 pated from (a) the 低 low temperature 温度质子 proton conductivities 电导率 of the 前体 precursor 酸 acids, [22] 和 and (b) from the realization that, due to the 平移 translational 度 degrees of 自由度 freedom being 受到限制 restricted, the 热 heat 容量 capacity, and 和 hence 因此 also 还 the rate 速率 of change 变化 of entropy 熵 with temperature, must 必须 be 更低 lower. 方程 Equations of the Adam Gibbs 类型 type [27] 温度 then 然后预测 predict a 小 smaller 温度 temperature 系数 coefficient for 传输 transport properties 性能 than are 典型 typical of glassforming liquids 液体 (such 如 as the standard 标准 nonaqueous 非水电解质 electrolyte seen in 图 Figure 1). To gain insight 深入了解 into the 热力学 thermodynamic 特性 character of the 新 new materials 材料 of 图 Figure 1 我们转向 we turn to 标准 standard (20 K min 1 ) 差 differential 扫描 scanning 量热 calorimetry (DSC) scans 扫描 on a sample 样品 of the product 产品 Li 4 Si(SO 4 ) 4. Figure 图 2 显示 shows that the 初始 initial downscan from 室 room temperature 显示 reveals a glass 玻璃转变 transition 典型 typical of glassforming 塑料 plastic 晶体 crystals, [7] at 接近 close to 90 C (see 参见 the inset Figure 1. Conductivities of the Li + 导电 conducting 塑料 plastic 晶体 crystals of 本 this 研究 study (identified 确定 in the 图例 legend), 相比 compared with those of 先前 previous state-ofthe-art 材料 materials. Solid 和 and dashed 线 lines 最适 best 适合 fitting the 电导率 conductivities of 三种 three of the Li [4] 10 GeP 2 O 12 type 型 superionic 超离子晶体 crystal phases 相 of 最近 recent 工作 work [5] are identified by 组成 composition 标记 labels.the thick dotted 黑 black 线 line, 和 and metatable extension 延伸 to 25 C, is the recent 最近 NaCB 9 H 10 rotator phase. 相 [17] The solid red 红色曲线 curve is the 标志性 landmark 数据 data of Kamaya et al. [4] and the 黑色 black dashed 线 line, extending 延伸 to 50 C 仅 only, is the standard 标准电解质 electrolyte [25] of 目前 current Li battery 电池技术 technology. The data 数据 for the 部分 partly 结晶 crystallized glass 玻璃 of ref. [3] lie slightly 略 below the highest 最高 curve 曲线 for the chlorinated 氯化 sample. 样品 The 短 short thick 黑色 black cuve is for LiTFSI in succinnonitrile as solvent. 溶剂 [6] The T g for reorientations (see 见图 Figure 2) in Li4 is at 88 C. Figure 2. DSC thermograms of the 塑料 plastic 晶体 crystal Li 4 Si(SO 4 ) 4, (Li4) during cooling 冷却 (blue 蓝色 curve 曲线 starting 开始 at ambient) 环境和 and 加热 heating 红色曲线 red curve 终止 terminating in phase 相 transition 相变 (exotherm at 85 C) to an ordered 有序 phase. 相随后 Subsequent (dashed 线 lines) 冷却 cooling 和 and 加热 heating 曲线 curves show 显示 the absence of 玻璃 glass 转变 transitions 和 and a 小 small 吸热 endothermic 效应 effect of 未知 unknown 来源 origin. The coincidence of the exotherm with the loss 损失 of 导电 conductivity due to the ordering 相 phase 相变 transition, is well 很好 illustrated 说明 in the superposition 叠加 diagram 图位于 located in the 支持 Supporting 信息 Information (3 of 7)

4 for 更好 better 明确 clarity of the temperature 温度 for the 热 heat 容量 capacity downjump) which is 确认 confirmed by the 更 more sharply 明确定义 defined upjump on the 再加热 reheating 扫描 scan. The 热 heat 流 flow 保持 remains 稳定 steady until 92 C when there is a 突然 sudden exotherm, obviously due to a 相 phase change to a 更 more 稳定 stable (nonrotator) 状态 state. The 随后 subsequent cooling 冷却 run 运行 (dashed 线 line) shows 显示 that the 玻璃 glass transition 转变 is 现在 now absent 不存在 as is 证实 confirmed in the 最终 final 加热 heating 运行 run 也 (also dashed line). 线我们 We were 无法 unable to 恢复 restore the 塑性 plastic 状态 state by 加热 heating to higher 更高温度 temperatures, 可能 probably because 因为 of 分解 decomposition. The stabilization 稳定 of the 塑性 plastic 状态 state by 二元 binary 混合 mixing (in 类似 analogy to the age-old 老 generation 一代 of glassforming ability 能力 in a single 个组件 component by 混合 mixing with 第二 second 和 and 第三 third 个组件 components), 将 will be discussed 讨论和 and 说明 illustrated later. To 确认 confirm the 完全 complete 去除 removal of 酸 acid 质子 protons from the target 目标锂 lithium 盐 salts, we 我们使用 used 1 H MAS NMR 光谱 spectra to 显示 show that the 尖锐 sharp 质子 proton 共振 resonance 特征 characteristic of the superprotonic 酸 acid had been 消除 eliminated by the LiNH 2 固 solid-state 态酸 acid base 碱反应 reaction (see 见图 Figure S1, 支持 Supporting 信息 Information). 同样 Likewise, comparison 比较 of the Raman 拉曼 spectra 光谱 of the 酸 acid 前体 precursor to Li4 和 and 液体 liquid H 2 SO 4 表明 shows that the split 共振 resonance at cm 1 2 characteristic 特征 of the SO 4 阴离子 anion, is completely 完全 missing from the 光谱 spectrum of the 酸 acid 前体 precursor (H4 [17] ) of the 锂 lithium 盐 salt Li4 (see 参见图 Figure S2, Supporting 支持信息 Information). NMR 光谱 spectroscopy is 有价值 valuable, also, 也 for physical 物理 characterization of 固体 solid 电解质 electrolytes. While 虽然 narrow 窄 resonances 共振 in 常规 con- 表征 ventional solid 固体 materials 材料 can 可以仅 only be 获得 obtained by 魔 magic 角 angle 旋转 spinning 策略 strategies, in systems 系统 like those of the 本 present 研究 study with configurational 动力学 dynamics on 短 short 时间 time 尺度 scales, a 形式 form of 运动 motional narrowing 变窄 can 可以 result in 尖锐 sharp NMR 系 lines using 仅 only 静态 static NMR. For 例如 example, in LiBH 4 both 快速 rapid BH 4 reorientation (timescale 时间尺度 s [12] 和 and 高 high Li 迁移率 mobility in the 稳定 stable phase 相 above 115 C, lead 导致 to almost 几乎 liquid-like 液体一样 line 线 shapes for the 7 Li resonances. [28] 我们 We 发现 find the 相同 same for the 7 Li resonance 谐振 in 我们 our 塑料 plastic 晶体 crystal 系统 systems. In the SI, 数据 data for Li4 are 比较 compared with those for the 固体 solid hydrate 水合物 of lithium 锂硫酸 sulfate studied 研究 under 相同 identical 条件 conditions, as 证据 evidence of the 快速 fast Li + dynamics. 动力学我们 We 还 also 显示 show a 类似 similar 窄 narrow 7 Li line 线 for the case of the trimethoxy plastic 塑料 crystal. 晶体 Detailed 详细 studies 研究 including 包括比较 comparisons of 7 Li + NMR and 和 conductivity 电导率 relaxation 弛豫时间 times, will 将 be the 主题 subject of future 未来出版物 publications. To be 适用 suitable for a 电池 battery 应用 application, it is necessary that there be a 良好 good 接触 contact between the 电解质 electrolyte and 和 the 源 source of 锂 lithium 离子 ions (lithium 锂金属 metal 或 or 替代 alternative 源 source 如 such as Li(gr) or 或 Li 4 Si), and 和 especially 特别是 at the sink for the Li ions 离子 within the 特别 particular 阴极 cathode of 感兴趣 interest. 由于 Since the LiCoO 2 阴极 cathode is one 一 of the 最 most 熟悉 familiar 和 and 可靠 reliable 阴极 cathodes, 我们选择 we chose 它 it for our 我们的初始 initial 测试 testing. 由于 Since the 电解质 electrolyte is a 软 soft solid 固体 it 其 is simple to force it 其 into the 微孔 micropores of a 标准 standard 细胞 cell separator, 分离器 such 如 as Celgard. 因为 Because if 它 its 更高 higher 电导率 conductivity, we 我们选择 chose trimethyl as the 电解质 electrolyte, notwithstanding 尽管 its 它更高 greater propensity 三甲基 for 再结晶 recrystallization to a less-conducting 导电 phase. 相 In 事实 fact, the sequestration 隔离 in the Celgard micropores 微孔似乎 seems to 稳定 stabilize the high-conducting 高导电 phase. 阶段 We 我们 performed the 填充 filling of the 微孔 micropores of the Celgard in a 低 low 湿度 humidity 手套 glove 箱 box (<0.1 ppm H 2 0 and <0.1 ppm O 2 ) by spreading the 凝胶 gel-like 电解质 electrolyte on the Celgard 表面 surface (resting on the 底 base of an agate mortar) 并 and 施加 applying 压力 pressure with the pestle until the 颜色 color of the 最初 initially 白色 white Celgard had 完全 completely transformed 转变 to a 半透明 semitransparent 外观 appearance, due to the 减少 reduction in 光 light 散射 scattering from the 最初 originally empty 空 pores. The 锂 lithium 箔 foil, 电解质 electrolyte-filled 填充 Celgard 隔膜 separator, 和 and cathode 阴极 film 膜 were 然后 then pressed 一起 together in a 纽扣 button 电池 cell which was sealed 密封 in the drybox environment, 环境 and 和 then 然后置 set in a vice to cure 固化 overnight. 过夜 Results 结果 for a 阴极 cathode 半 half-cell 电池 with LiCoO 2 阴极 cathode are shown 显示 in 图 Figure 3. The 程度 degree of 可逆性 reversibility, judged 判断 by peakto-peak 峰值 voltage 电压 separation 分离 of essentially 基本 the 理论 theoretical 可逆 reversible 值 value (0.059 V), is to be emphasized. 强调 It is 暗示 implied that reliable 可靠离子 ionic 接触 contact between 电解质 electrolyte 和 and 阴极 cathode 材料 material, often 通常发现 found to be a 问题 problem in 电池 batteries with 固体 solid 电解质 electrolytes (e.g., the superionic 超离子 glass 玻璃 or 或 crystal 晶 of Seino et al. [3] ) will 会 not 不 be a 问题 problem with 我们的电解质 our electrolytes. A 测试 test of stability 稳定性 to 阳极 anode cycling 循环 (stripping 剥离 of Li 和 and subsequent 沉积 deposition) was carried 进行 out using a 对称 symmetric Li 随后金属 metal 纽扣 button 电池 cell with freshly 制备 prepared 三甲基 trimethyl 塑料 plastic electrolyte, the high 高导电 conductivity of the 电解质 electrolyte being 反映 reflected 电解质 in the 低 low 电池 cell 阻抗 impedance, 仅 only 10 Ω. 也许 Perhaps 因为 because of 此 this, the PARSTAT 2273 voltammogram 伏安图 was very 非常 noisy 嘈杂 and the 测试 test 失败 failed before the 第一 first 周期 cycle could be 完成 completed. 然而 However, the trace 获得 obtained had both 剥离 stripping 和 and 沉积 deposition 电导率 conductivity 极值 extremes, measured 测量 in fractions 分数 of amps, at a scan 扫描速率 rate of 20 mv s 1. A 比较 comparison of 该 this scan 扫描 with one from the 文献 literature, in which the 电流 current 流动 flowing was 四个 four orders of 个数量级 magnitude 低 lower (in the 分数 fractional ma range) 范围 is given 给出 in the 支持 Supporting 信息 Information. 它 It 增加 adds credence to the view that our 我们的噪声 noise 问题 problem 可能 might 能 have been 引起 caused by the 特殊 exceptional 电流 current flowing. The main 主要问题 problem 面临 facing the 使用 utilization of the 本 present 电解质 electrolytes concerns 问题 the 可能性 possibility of 重结晶 recrystallization to 有序 ordered, 低 lower-conducting 导电 phases, 相 as is illustrated in the thermogram of 图 Figure 2. 幸运 Fortunately, there is a 解决方案 solution to 这个 this 问题 problem, 但 but 一个 one that 需要 requires detailed 详细研究 studies that 有 have so 目前 far been 只 only 部分 partially executed. 执行 The principle 原理 is one that has been 用 used to 永久 permanently 稳定 stabilize the 塑料 plastic 晶体 crystal (rotator) phase 相 of succinonitrile against 重结晶 recrystallization to its 其 ordered 有序 phase. 相 [20] 这 This is 影响 affected as illustrated in 图 Figure 4a. It 它 invokes the same 相同 principle of entropic 熵稳定化 stabilization of a 均匀 homogeneous 溶液 solution over 原理 the 单 single 相 phase, as in the 稳定化 stabilization of the 溶液 solution 相 phase of a 二元 binary eutectic 共晶 system 体系 to permit 允许玻璃 glass 形成 formation. 其 It is 非常 very 熟悉 familiar phenomenology 现象学 in the 情况 case of 简单 simple 共晶 eutectic 体系 systems in which the 熔 melting 点 points of 两种 two 结晶 crystalline 组分 components are 降低 lowered due to the stabilization 稳定 of the solution 溶液相 phase by entropy 熵 of 混合 mixing 相结合 coupled with the 不溶性 insolubility of the 组分 components in the 另一 other s crystal 晶体 lattice. 晶格 It 它 is less familiar 熟悉 in the 情况 case of 塑料 plastic 晶体 crystals but 但 has been 用 used 成功 successfully to eliminate 消除 the 转变 transition of succinonitrile to an 有序 ordered 固体 solid by 混合 mixing with the look-alike molecule 分子 glutaronitrile which has 一个 one additional 额外亚甲 methylene 连接 link. 它 It 工作 works 同样 equally well with the 第二 second 组分 component 丙二腈 malononitrile, which has one 一个少 less 亚甲 methylene link (List 表 and 和 Angell, unpublished 未发表 work 工作 DOE progress 进展报告 report 1985). When more than 10 摩尔 mole% of the 分子 molecule glutaronitrile is 加入 added to the 塑料 plastic 晶体 crystal succinonitrile, the rotator 相 phase can 不 no longer 产生 generate 核 nuclei to 结晶 crystallize, and 并 a wide 各种 range of stabilized rotator phase 相玻璃 glass-forming 形成 character 特性 is opened 开辟 up (see 见图 Figure 4a). In 我们 our 自己 own 研究 studies, we 我们发现 found a 类似 similar 效果 effect in the 混合 mixing of 两种 two 不同 different 制剂 preparations that 使用 used SiCl 4 as starting 起始材料 material. 这些 These were intended 旨在 to 产生 produce 分子 molecules (4 of 7)

5 Figure 3. 证明 Demonstration of 稳定 stable 循环 cycling (after 第一 first 循环 cycle) for Li 嵌入 intercalation/de-intercalation 嵌入 in LiCoO 2 阴极 cathode in Li 箔 foil/trimethylsilyl 三甲基甲硅烷 Li sulfate/ 硫酸 LiCoO 2 构型 configuration, in 纽扣 button 电池 cell assembly. 电池 Cell 阻抗 impedance was higher than in 对称 symmetric 电池测试 cell test and 电流 current 流动 flowing was 多 much 低 lower. 注意 Note that the 峰 peak-to-peak 峰 separation is 接近 close to the 真实可逆性 true reversibility 值 value (0.059 V). Figure 4. a) 相 Phase 图 diagram for the 二元 binary 体系 system succinnonitrile + glutaronitrile showing 显示 how 如何 small 少 amounts 少量 (10 mol%) of the second 第二 component 组分 can 完全 completely suppress 抑制 the 结晶 crystallization of the 有序 ordered 相 phase Reproduced from ref. [20] with permission 许可 of American 美国 Institute of 物理学 Physics. b) 时间 Time 依赖性 dependence of 电导率 conductivity at 不同 different 温度 temperatures for Li4 单独 alone (solid 线 lines) 和 and also after 混合 mixing (by 球 ball 磨 milling) at mass 质量分数 fraction 1:1 (dashed 线 lines, 相同 same 颜色 colors, 和 and 符号 symbols), [29] with a second 第二 Li4 sample 样品制备 prepared with a 不同 different 方案 protocol. In the 第一 first 情况 case, the 电导率 conductivity 下降 decreased 缓慢 slowly over the period 时间 of a 一周 week, presumably 可能 due to slow 缓慢 transformation 转变 to the ordered 有序状态 state, while 而 the mixed 混合 case 情况 showed 表现 the opposite 相反行为 behavior, initially 最初 increasing 增加 rapidly, 迅速 and then 然后 settling into a steady 稳定 state 状态 of 高 high 电导率 conductivity stable 稳定 against repeated 反复 excursions to 100 C (5 of 7)

6 with different 不同数量 numbers of 残余 residual Cl 配体 ligands, but 但 we 我们现在 now know, 知道 from the quenched 反应 reaction 实验 experiments 描述 described in ref. [22] that they 他们导致 lead to Li4, probably 可能 with 不同 different 低聚 oligomeric components. 成分图 Figure 4b 表明 demonstrates that the 第一 first of 这些 these Li4 preparations 制剂 leads 导 to a 产物 product of 高 high 初始 initial conductivity 电导率 which then 然后 decreases 降低 with time 时间 to 值 values some two 两个 orders of 个数量级 magnitude 降低 lower, presumably 可能 due to 缓慢 slow crystallization 结晶 to an 有序 ordered 相 phase. By contrast, 相反 a mixture 混合物 of separate 单独制剂 preparations of Li4, 信 believed to 不同 differ in 低聚物 oligomer content, 含量 shows 表现出 the 相反 opposite 行为 behavior and 并 stabilizes with conductivities of about 10 ms cm 1 at 环境 ambient 温度 temperature ( S cm 1 at 40 C). In 这种 this 混合物 mixture, there is 没有迹象 no sign of a 转变 transformation to an 有序 ordered 相 phase even with 反复 repeated excursions 偏移 to 100 C on 连续 successive 天 days. Clearly, this 这 should 应该 be the 主题 subject of 进一步 further 研究 research 旨在 aimed at 获得 obtaining a 精确 precisely 定义 defined 锂 lithium 甲硅烷基硫酸 silyl sulfate 版本 version of 图 Figure 4a. The best 最好情况 case would be one 基于 based on 混合 mixed methylphenylsilanes (e.g., trimethylphenyl silane 硅烷 and 和 dimethyldiphenyl 硅烷 silane) starting 起始 materials, from which 纯 pure 甲基 methyl 甲硅烷基氢 silyl hydrogen sulfates 硫酸 (probably 可能 both liquid 液体 acids) 酸 could 可能 be 获得 obtained 和 and then 然后锂化 lithiated. In the 介绍 Introduction, 我们提到 we mentioned the 潜在 potential 优势 advantage of 塑料 plastic 晶体 crystals with respect to 玻璃 glasses, which comes with the possibility of 保持 maintaining solidity to 温度 temperatures well above the 玻璃 glass 转变 transition 温度 temperature (above which 玻璃 glassy solid 固体电解质 electrolytes would flow). 明显 Clearly, the 阳离子 cation 运动 motion in our 我们材料 materials is, by 构造 construction, decoupled from the 阴离子 anion diffusivity, but 但 the question 问题 of whether 是否 or not 它 it is decoupled from the 阴离子 anion reorientational motions 运动 is not 解决 addressed so far. 目前 In 一般 general, we 我们可能 might 期望 expect that 任何 any 耦合 coupling will be very system-dependent. 系统 For 例如 instance, reorientations 重新定向应该 should 发生 occur on a 更短 shorter 时间 time 尺度 scale than 电导率 conductivity 位移 displacements (to be obtained 获得 from the 电导率 conductivity relaxation 弛豫 time) 时间 when 阴离子 anions are 对称 symmetrical and 并紧凑 compact 如 like BH 4 (for which 重新定向 reorientations 可以 can 明显 evidently 发生 occur on the 皮秒 picosecond 时间 time 尺度 scale), [12] 而 while the 相反 opposite may 可能 be the 情况 case when 阴离子 anions are 较大 larger 并 and less 对称 symmetrical. Without 定量 quantitative information 信息 on the 重新定向 reorientation time 时间 for the 阴离子 anions, there can 可 be little more to 说 say at 该 this 时间 time, but 但 it 它 is clearly a subject 主题 for further 进一步工作 work in 该 this 领域 area. In summary, we 我们已 have described 已经描述 and 并描述 characterized a 特殊 special 类 class of 超离子 superionic 固体 solid 电解质 electrolyte in which the 唯一 only 移动 mobile 物种 species is the 碱 alkali cation 阳离子 and 并 the 电导率 conductivity can 可达到 reach 值 values as high 高 as 10 ms cm 1 at ambient temperature, 但 but somewhat below that 可获得 obtainable with NaCB 9 H 10 rotator 相 phase. [17] 虽然 While these 这些材料 materials are 高 highly 导电 conductive 它们 their 机械 mechanical 状态 state is solid 虽然 though with 低 low 剪切 shear 模量 modulus 这些 such that 它们 they 可以 can be 掺入 incorporated in supporting 基质 matrices of 所需 desired 机械 mechanical properties 性能 by 简单 simple 机械 mechanical 压力 pressure. 它们 Their 可塑性 plasticity has been 已经证明 shown to be 相容 compatible with 良好 good 电 electrical 接触 contact with solid 固体阴极 cathodes, 并 and almost 几乎 ideally 理想可逆 reversible intercalation/ 嵌入 de-intercalation 嵌入 kinetics, 动力学 has been demonstrated. 证明 We 我们希望 expect that the 材料 materials 报道 reported 这里 here, 虽然 while 具有 displaying many 许多有用 useful 性能 properties, will be only 只 the forerunners of much 许多 better 更好 and more 更 reliable 可靠 versions 版本 of the 同 same 类 class of 碱 alkali metal 金属导体 conductors. 实际 Indeed, 我们 our 第一 first 暗示 hint of 它们 their 存在 existence was obtained 获得 in a 研究 study of 钠 sodium 离子 ion 导体 conductors. Clearly, 我们 we should 应该 be 能够 able to 转变 turn the 准备 ready recrystallization 重结晶 of the trimethyl 化合物 compound (to an 有序 ordered 相 phase) to advantage to 获得三甲基 obtain a 晶体 crystal structure 结构 that will 将 aid 有助 in the 理解 understanding of the 电解质 electrolyte function. 功能 Experimental 实验 Section 部分 LiSi(CH 3 ) 3 (SO 4 ), Trimethy(lithium 锂三甲基甲硅烷 trimethylsilyl sulfate): 硫酸 Trimethylphenylsilane (99%, Sigma-Aldrich) was added 加入 to 硫 sulfuric acid 酸 (99.999%, Sigma-Aldrich) in a 1:1 mol ratio 比 under argon 氩气气氛 atmosphere (with slight excess 过量 of 硅烷 silane). The 混合物 mixture was 保持 kept under 恒定 constant stirring 搅拌 for 30 min. The 最终 final 产物 product is a 黄色 yellow 液体 liquid. NMR: 1 Hδ = 0.37, ppm; 13 Cδ = 0.67 ppm; 29 Siδ = 锂 Lithium amide was added 加入 to the liquid 液体 in a 1:1 摩尔 molar 比 ratio and 并 left stirring 搅拌 for 48 h under inert 惰性 atmosphere. 气氛然后 Then the 产物 product was homogenized in an agate mortar and 和 pestle, resulting 得到 in a 柔软 soft waxy 固体 solid. The waxy solid 固体 was 掺入 incorporated in Celgard 3401 by applying 施加 pressure 压力 with the mortar and 和 pestle. The neutralization 中和 step 步骤可以也 can also be 进行 performed, with 较少 less 可靠性 reliability, using LiCl, when the reaction 反应 is less 较少剧烈 vigorous but 但 the elimination 消除 of all 所有质子 protons less 较少 certain (and 和也 also the 反应 reaction 产物 product, HCl, 较少 less 欢迎 welcome, in the low 低 humidity, 湿度 low 低 p O2 drybox). LiSi(CH 3 O) 3 (SO 4 ), Trimethoxy: Trimethoxyphenylsilane (97%, Sigma- Aldrich) was added 加入 to 硫 sulfuric acid 酸 (99.999%, Sigma-Aldrich) in a 1:1 mol ratio 比 under 氩气 argon 气氛 atmosphere (with slight 过量 excess of 硅烷 silane). The mixture 混合物 was 保持 kept under 恒定 constant 搅拌 stirring for 30 min. The 最终 final 产物 product is a 白色 white, opaque 不透明固体 solid 和 and a 无色 colorless, 透明 transparent 液体 liquid, which was determined 测定 (via 1 H NMR) to be a 混合物 mixture of 苯 benzene, 甲醇 methanol, 和 and starting 起始硅烷 silane. Lithium amide 酰胺 was added 加入 to the 固体 solid in a 1:1 molar 摩尔比 ratio and 和 homogeneized in an agate mortar and 和 pestle, resulting 得到 in a soft 柔软 waxy solid. 固体 Li 4 Si(SO4) 4, Li4: Preparation 制备描述 described 其他地方 elsewhere. [15] Supporting 支持信息 Information Supporting 支持信息 Information is available from the Wiley 在线 Online 图书馆 Library 或 or from the author. 作者 Acknowledgements 致谢 This 这项项研究 research was 支持 supported by the 办公室 Office of 车辆 Vehicle 技术 Technologies of the U.S. Department of 能源 Energy under 合同 Contract No. DE-AC02-05CH11231, Subcontract No under the 电池 Batteries for 先进 Advanced Transportation 运输技术 Technologies (BATT) Program, 计划 in its 初始 initial 阶段 stages, 尽管 while the concluding 合成 synthetic 突破 breakthroughs, conductivities 电导率 NMR and 和 Raman 拉曼 characterizations, 表征 and 和 half-cell 半电池 studies 研究 of both 前体 precursor hydrogen sulfate 硫酸酸 acids 和 and 最终 final 锂 lithium 盐 salts, were 支持 supported by the DOD-ARO fuel 燃料电池基础 cell basic 研究 research 计划 program under Grant No. W911NF The authors 作者 would like to acknowledge the LeRoy Eyring 中心 Center for 固 Solid State 态科学 Science and 和 the 磁 Magnetic 共振 Resonance 研究 Research 中心 Center at 亚利桑那 Arizona State 态大学 University for the use 使用 of 他们 their 设施 facilities. Conflict 冲突 of 利益 Interest The authors 作者 declare 没有冲突 no conflict of 利益 interest. Keywords 关键词 impregnable 固体 solid 电解质 electrolytes, lithium 锂离子塑料 ion plastic 晶体 crystal, 可逆 reversible lithium 锂 intercalation 嵌入 Received: 可 May 1, 2018 修订 Revised: July 20, 2018 发布 Published 在线 online: (6 of 7)

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