TWI787212B - 用於鋰硫電池的電極 - Google Patents
用於鋰硫電池的電極 Download PDFInfo
- Publication number
- TWI787212B TWI787212B TW106138878A TW106138878A TWI787212B TW I787212 B TWI787212 B TW I787212B TW 106138878 A TW106138878 A TW 106138878A TW 106138878 A TW106138878 A TW 106138878A TW I787212 B TWI787212 B TW I787212B
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- Prior art keywords
- lithium
- polymer
- sulfur
- current collector
- sulfur battery
- Prior art date
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 42
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- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
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Classifications
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- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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Abstract
根據本揭露內容,存在用於鋰硫電池的電極。電極包括沉積在集流體上的基質,其中基質包括導電材料、電活性硫材料和黏合劑,黏合劑包含被交聯以形成交聯聚合物網路的聚合物。
Description
本發明涉及用於鋰硫電池的電極。本發明還涉及生產這種電極的方法,以及包括這種電極的鋰硫電池。
典型的鋰-硫電池包括由鋰金屬或鋰金屬合金形成的陽極(負電極)和由元素硫或其它電活性硫材料形成的陰極(正電極)。硫或其它電活性含硫材料可以與諸如碳的導電材料混合,以改進其導電性。碳和硫可以被研磨,並且然後與溶劑和黏合劑混合以形成漿料。可以將漿料施加到集流體,並且然後乾燥以去除溶劑。所得結構被壓延以形成複合結構,該複合結構被切割成期望的形狀以形成陰極。隔板可以放置在陰極上,並且電解質可以被施加到隔板以潤濕陰極和隔板。可以將鋰陽極放置在隔板上以形成電池堆(cell stack)。
在描述本發明的特定實例之前,應理解,本揭露內容不限於本文所揭露的特定的電池、方法或材料。還應理解,本文使用的術語僅用於描述特定的實例,並且不意圖是限制性的,因為保護範圍將由申請專利範圍第及其等同內容限定。
術語「蛋白質」或「多肽」或「肽」可互換使用,並且是指由氨基酸鏈組成的分子,而與特定作用模式、尺寸、三維結構或來源無關。
本文使用的「明膠」和「似明膠蛋白」指無論是通過傳統的方法或重組或本質上的生物合成提取的任何明膠,或指具有明膠的至少一種結構和/或功能特性的任何分子。該術語涵蓋包含在明膠產物中的多於一種多肽的組成以及對明膠材料有貢獻的單個多肽二者。因此,關於本發明使用的術語明膠涵蓋包含明膠多肽的明膠材料以及單個明膠多肽二者。
如本文描述的「交聯劑(crosslinking agent)」指包含交聯物(crosslinker)的組合物。如本文使用的「交聯物」指反應性化合物,該反應性化合物能夠在有機分子中引入共價分子內橋和共價分子間橋。
在描述和要求保護本發明的電池和方法時,將使用以下術語:單數形式「一(a)」、「一(an)」和「該(the)」包括複數形式,除非上下文另有明確規定。因此,例如,提及「一陽極」包括提及一或複數這樣的元件。
根據本發明,存在用於鋰硫電池的電極。電極包括沉積在集流體上的基質,其中基質包括導電材料、電活性硫材料和黏合劑,該黏合劑包含被交聯以形成交聯聚合物網路的聚合物。
在另一方面,本發明還提供了鋰硫電池,該鋰硫電池包括如上所述的電極。電極較佳地是電池的陰極。陽極可以是包括鋰金屬例如純鋰金屬或鋰金屬合金的陽極。其它合適的陽極材料包括適用於鋰離子電池中的陽極,例如矽陽極或石墨陽極。
在另一方面,本發明提供了生產用於鋰硫電池的電極的方法。該方法包括將電極混合物沉積到集流體上,該電極混合物包含導電材料、電活性硫材料和包含聚合物的黏合劑,由此聚合物被交聯以在集流體上形成交聯聚合物網路。
聚合物可以在被沉積在集流體上之前交聯,或可以在被沉積在集流體上之後聚合,例如通過暴露於交聯劑。
通過使聚合物交聯,導電材料和電活性硫材料可以通過交聯聚合物網路被保持在合適位置。這種交聯聚合物網路可以改進電極的結構完整性,有助於在鋰硫電池的充電和放電迴圈期間所形成的帶電荷的物質在電池充電和放電時保持與集流體電接觸。有利地,這可以導致鋰硫電池的迴圈壽命的改進。黏合劑
黏合劑包含被交聯以形成聚合物網路的聚合物。聚合物可以是任何可交聯的聚合物。例如,聚合物可以包含可以被交聯的官能團。合適的官能團的實例包括胺基、醯胺基、羰基基團、羧基基團、醚基、硫醚基和羥基基團。在一種實施方案中,聚合物通過選自胺、醯胺、羰基、羧基、醚、硫醚、亞胺和羥基中的至少一種的官能團交聯。在較佳的實施方案中,聚合物包含氨基酸殘基。交聯可以通過這些殘基中的一或複數發生。
較佳地,聚合物是生物聚合物。生物聚合物選自多肽和多糖。合適的多肽包括明膠、膠原和膠原模擬肽。合適的多糖包括殼聚糖、透明質酸鹽和透明質酸。在較佳的實施方案中,聚合物是明膠。
在一種實施方案中,聚合物是聚丙烯醯胺。
聚合物可以形成沉積在集流體上的基質的從0.01重量%至50重量%。較佳地,聚合物形成沉積在集流體上的基質的從0.01重量%至20重量%。更佳地,聚合物可以形成沉積在集流體上的基質的從0.1重量%至15重量%,例如1重量%至10重量%。
聚合物的重量與導電材料(例如碳)和電活性硫材料(例如硫)的重量的比可以是0.01-10:30-60,較佳地0.1-5:35-55。更佳地1-3:40-50。在一種實施方案中,聚合物與導電材料(例如碳)的重量比可以是0.01-15:5-35,較佳地0.1-10:8-25,更佳地1-5:10-15。在一種實施方案中,聚合物與電活性材料(例如硫)的重量比可以是0.01-20:20-50,較佳地0.1-15:25-45,更佳地1-10:30-40。交聯劑
聚合物可以使用任何合適的方法交聯,例如通過加熱或通過暴露於照射,例如UV輻射。例如,在使用諸如明膠的生物聚合物時,可以通過加熱使聚合物交聯。
在一些實例中,聚合物通過使交聯劑與聚合物反應來交聯。可以採用任何合適的交聯劑。
合適的交聯劑包括醛。合適的醛的實例包括甲醛、二醛、戊二醛、甘油醛和糠醛。在一些實施方案中,酮被用作交聯劑。合適的酮包括丙酮、二縮醛和其它二酮,例如戊二酮,例如氯戊二酮。
交聯劑的其它實例包括碳二亞胺、尿素、乙二醛、聚縮甲醛、亞胺、二環氧化合物和二異氰酸酯。還可以使用酶,例如轉穀氨醯胺酶。在另一種實施方案中,交聯劑選自雙(2-氯乙基脲);2-羥基-4,6-二氯-1,3,5-三嗪;在US 3,288,775中揭露的反應性含鹵素化合物;在US 4,063,952和US 5,529,892中揭露的氨基甲醯基吡啶鎓化合物,其中吡啶環攜帶硫酸酯基團或硫酸烷基酯基團;二乙烯基碸和S-三嗪衍生物例如2-羥基-4,6-二氯-s-三嗪。合適的交聯劑的又另外的實例包括1-乙基-3-[3-二甲基氨基丙基]碳二亞胺鹽酸鹽(EDC或EDAC)。
交聯劑可以任何合適的量添加。例如,交聯劑與黏合劑中聚合物的重量比可以是0.01-20:10-200,較佳地0.1-10:20-100,更佳地1-5:10-50。
聚合物可以通過任何合適的方法進行交聯。例如在一種實施方案中,包含導電材料、電活性硫材料和黏合劑的電極混合物可以分散在溶劑(例如水或有機溶劑)中,以形成被施加到集流體的漿料。漿料可以被乾燥並且所得結構被壓縮以形成沉積在集流體上的基質。可以將交聯劑施加到基質上以使基質中的聚合物交聯。交聯劑可以作為單獨的溶液施加,或者與電解質溶液混合來施加,該電解質溶液隨後在電池的組裝期間與電極接觸。
在一種可選擇的實施方案中,交聯劑可以在其沉積在集流體上之前或之後被添加到漿料。
在又另一種備選方案中,聚合物可以在被併入到電極混合物中之前被交聯。包含導電材料、電活性硫材料和交聯聚合物黏合劑的所得混合物可以分散在溶劑(例如水或有機溶劑)中,以形成被施加到集流體的漿料。漿料可以被乾燥並且所得結構被壓縮以形成沉積在集流體上的基質。
交聯反應可以通過加入水分、用例如UV的照射或通過升高的溫度來增強。電活性硫材料和導電材料
基質包括電活性硫材料和導電材料的混合物。該混合物形成電活性層,該電活性層被放置成與集流體接觸。
電活性硫材料可以包括元素硫、基於硫的有機化合物、基於硫的無機化合物和含硫聚合物。較佳地,使用元素硫。
導電材料可以是任何合適的固體導電材料。較佳地,該固體導電材料可以由碳形成。實例包括炭黑、碳纖維、石墨烯和碳奈米管。其它合適的材料包括金屬(例如薄片、填料和粉末)和導電聚合物。較佳地,使用炭黑。
電活性硫材料可以以60重量%至90重量%、較佳地65重量%至85重量%、更佳地70重量%至80重量%的量存在於沉積在集流體上的基質中。
導電材料可以以10重量%至45重量%、較佳地15重量%至35重量%、更佳地20重量%至25重量%的量存在於在沉積在集流體上的基質中。
電活性硫材料與導電材料的重量比可以是0.01-10:10-50、較佳地0.1-5:15-45、更佳地1-5:20-35。鋰硫電池
本發明的電化學電池可以是任何合適的鋰硫電池。電池典型地包括陽極、電解質以及由本文中描述的電極形成的陰極。陽極可以由鋰金屬或鋰金屬合金形成。較佳地,陽極是金屬箔電極,例如鋰箔電極。鋰箔可以由鋰金屬或鋰金屬合金形成。
隔板可以被放置在陽極和陰極之間。可以將電解質引入到電池中以潤濕陰極和隔板。在一種實施方案中,在陽極被放置在隔板上之前,隔板被放置在陰極上並用電解質潤濕。電解質可以例如通過包覆或噴塗被施加到隔板上。
電解質允許電荷在陽極和陰極之間傳遞。較佳地,電解質潤濕陰極的孔以及隔板的孔。在一種實施方案中,用於組裝電池的電解質包括交聯劑,該交聯劑可以使存在於黏合劑中的聚合物反應和交聯。上面提到了合適的交聯劑。當存在時,交聯劑可以以0.01重量%-10重量%、較佳地0.1重量%-1重量%的濃度存在於電解質中。
可以使用任何合適的電解質。電解質可以包含有機溶劑和鹽,例如鋰鹽。合適的有機溶劑包括醚、酯、醯胺、胺、亞碸、磺醯胺、有機磷酸酯和碸。實例包括四氫呋喃、2-甲基四氫呋喃、丙基丙酸甲酯(methylpropylpropionate)、丙基丙酸乙酯(ethylpropylpropionate)、乙酸甲酯、1,2-二甲氧基乙烷、1,3-二氧戊環、二甘醇二甲醚(2-甲氧基乙基醚)、三甘醇二甲醚、四甘醇二甲醚、丁內酯、1,4-二氧六環、1,3-二氧六環、六甲基磷醯胺、吡啶、二甲基亞碸、磷酸三丁酯、磷酸三甲酯、N,N,N,N-四乙基磺醯胺和碸以及它們的混合物。
合適的電解質鹽包括鋰鹽。合適的鋰鹽包括六氟磷酸鋰、六氟砷酸鋰、硝酸鋰、高氯酸鋰、三氟甲烷磺醯亞胺鋰、硼酸雙(草酸)鋰和三氟甲烷磺酸鋰。較佳地,鋰鹽是三氟甲烷磺酸鋰(lithium trifluoromethanesulphonate)(也稱為三氟甲烷磺酸鋰(lithium triflate))。可以採用鹽的組合。例如,三氟甲烷磺酸鋰可以與硝酸鋰組合使用。鋰鹽可以以0.1M至5M、較佳地0.5M至3M的濃度存在於電解質中。
隔板可以被放置在陽極和陰極之間。在本發明的電池中存在隔板的情況下,隔板可以包括任何合適的多孔基板,該多孔基板允許離子在電池的電極之間移動。隔板應當被安置在電極之間,以防止電極之間的直接接觸。基板的孔隙率應當為至少30%,較佳地,至少50%,例如,高於60%。合適的隔板包括由聚合物材料形成的網。合適的聚合物包括聚丙烯、尼龍和聚乙烯。非織造聚丙烯是特別較佳的。採用多層隔板是可能的。
結合本發明的特定的方面、實施方案或實施例所描述的特徵、整體、特性、化合物、化學部分或基團應被理解為適用於本文描述的任何其它方面、實施方案或實施例,除非與其相矛盾。本說明書(包括任何所附的申請專利範圍、摘要和附圖)中揭露的所有特徵和/或如此揭露的任何方法或製程的所有步驟都可以以任何組合來結合,除了這樣的特徵和/或步驟中的至少一些是相互排斥的組合之外。本發明不受限於任何前述實施方案的細節。本發明擴展至本說明書(包括任何所附的申請專利範圍、摘要和附圖)中揭露的特徵中的任何新的特徵或任何新的組合,或擴展至如此揭露的任何方法或製程的步驟的任何新的步驟或任何新的組合。
讀者的注意力被指向與關於本申請的此說明書同時或在關於本申請的此說明書之前提交的以及與本說明書一起對公眾查閱揭露的所有論文和檔,並且所有這些論文和檔的內容都通過引用併入本文。
然而,存在通過添加2%甲醛使明膠交聯的證據。在交叉點@3841秒觀察到模量的明顯變化。相位角從大約90°下降到2°,證實了凝膠結構的增加。實施例 1
在這個實施例中,碳和硫被碾磨並且與聚合物黏合劑和水混合以形成漿料,其中硫含量是75重量%,碳23重量%以及明膠黏合劑2重量%(在水中40-50重量%)。將含有丙酮作為交聯劑的溶液(水:交聯劑(2:1比率))作為溶劑添加到分散體,以形成具有20重量%固體含量的分散體。然後將該漿料施加到集流體,並且在35℃乾燥,以從被包覆的陰極除去溶劑,從而得到5.0 mAh·cm-2的表面容量。陰極用於組裝填充有基於醚的電解質的6S/5Li電池。
下面的第1圖示出了電池的放電性能,該電池以0.2C和0.1C倍率(分別放電-充電)迴圈並且與未添加交聯劑的電池相比。可以觀察到,即使兩種電池顯示出相似的初始放電容量值,但是使用交聯劑生產的電池以大約1100 mAh·g(S)-1的硫利用率隨著時間仍然保持穩定。另一方面,使用未交聯黏合劑組裝的電池在第三次迴圈後開始衰減(fading)。
使用交聯黏合劑所觀察到的改進,可以歸因於由聚合物黏合劑與交聯劑的反應引起的陰極的增強的結構完整性。這種交聯反應也被認為改進了對集流體的塗層黏附,降低了可能引起電池的過早衰減的分離(detchment)風險。實施例 2
陰極通過在集流體上沉積硫、碳和明膠的混合物來形成。從陰極切下二正方形(2×2 cm)。
在手套箱中,5滴福馬林(37%的甲醛水溶液與作為穩定劑的10%甲醇)施加到陰極樣品之一,並且靜置過夜。然後用棉簽進行刮擦試驗,並且顯示出福馬林處理的樣品比未處理的樣品具有更優越的陰極完整性和對集流體的黏附。實施例 3
進行一系列實驗以研究是否發生明膠與甲醛的交聯。
以振盪時間掃描模式(oscillation time sweep mode),使用TA Instruments DHR2流變儀來測量儲能模量/損耗模量(Storage/Loss Modulus)和相位角。明膠儲備溶液的製備:
稱取15克的來自冷水魚皮的明膠@45%(來自Sigma Aldrich G7765),放入100 cm-3的玻璃燒杯中,向其中添加15克去離子水,然後在IKA磁力攪拌器上混合持續5分鐘。明膠 / 甲醛溶液的製備
稱取3克製備的明膠溶液放入玻璃小瓶中,向其中添加0.036克甲醛溶液(來自Sigma Aldrich 252549),並且在IKA磁力攪拌器上混合,以得到2%溶液。流變測定
使用TA Instruments DHR 2流變儀來測量明膠/甲醛溶液的黏彈性性質,連同明膠儲備溶液作為基準。下面列出了流變儀參數和測試條件: 流變儀參數:
流變儀:TA Instruments DHR2流變儀
幾何結構:平行板40mm直徑
2小時@2%應變的振盪時間,1Hz頻率
珀爾帖板(Peltier Plate)溫度:40℃
結果:
依據振盪時間掃描,明膠儲備溶液的損耗模量和相位角存在小偏差。因此沒有交聯的證據。
本揭露內容的各方面僅通過實例的方式在附圖中被示意性示出,在附圖中: 第1圖示出了實施例1的電池的放電容量如何隨迴圈次數而變化。
Claims (14)
- 一種鋰硫電池,該鋰硫電池包括:一陰極,以及一陽極,該陽極包括鋰金屬或鋰合金,其中該陰極包括沉積在集流體上的一基質,其中該基質包括一導電材料、一電活性硫材料和一黏合劑,該黏合劑包含被交聯以在該基質中形成一交聯聚合物網路的一聚合物,其中該聚合物是一生物聚合物,以及其中該聚合物藉由選自胺、醯胺、羰基、羧基、醚、硫醚和羥基中的至少一種的官能團交聯;以及其中該電活性硫材料及該導電材料藉由該交聯聚合物網路被保持在合適位置。
- 如申請專利範圍第1項所述的鋰硫電池,其中該生物聚合物選自多肽和多糖。
- 如申請專利範圍第2項所述的鋰硫電池,其中該生物聚合物是一多肽,該多肽選自明膠、膠原和膠原模擬肽。
- 如申請專利範圍第1項所述的鋰硫電池,其中該生物聚合物是殼聚糖。
- 如申請專利範圍第1項至第4項中任一項所述的鋰硫電池,其中該聚合物藉由一交聯劑交聯。
- 如申請專利範圍第5項所述的鋰硫電池,其中該交聯劑選自環氧交聯劑、二乙烯基碸、二硫化碳、醛、酮、碳二亞胺和二異氰酸酯。
- 如申請專利範圍第6項所述的鋰硫電池,其中該交聯劑是甲醛或二異氰酸酯。
- 如申請專利範圍第1項至第4項中任一項所述的鋰硫電池,其中該基質包括0.01重量%至50重量%的該交聯聚合物。
- 如申請專利範圍第1項至第4項中任一項所述的鋰硫電池,其中該導電材料包含粒狀碳材料,並且該電活性硫材料包含元素硫。
- 如申請專利範圍第1項至第4項中任一項所述的鋰硫電池,其中該導電材料和該電活性硫材料分散在該基質中的該交聯聚合物網路中。
- 一種生產用於如申請專利範圍第1項所述的鋰硫電池的電極的方法,該方法包括:將一電極混合物沉積到一集流體上以包覆該集流體,其中該電極混合物包含一導電材料、一電活性硫材料和包含一聚合物的黏合劑;以及使該聚合物交聯,由此將包含一交聯聚合物網路的一基質沉積到該集流體上,其中該聚合物是一生物聚合物,以及其中該聚合物藉由選自胺、醯胺、羰基、羧基、醚、硫醚及羥基中的至少一種的官能團交聯。
- 如申請專利範圍第11項所述的方法,其中將包含該電極混合物和溶劑的漿料沉積到該集流體上。
- 如申請專利範圍第12項所述的方法,其中將一交聯劑添加到被包覆的集流體,以使該聚合物交聯。
- 如申請專利範圍第11項所述的方法,其中將一交聯劑添加到一電解質,該電解質隨後與被包覆的集流體接觸。
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