TWI738280B - 可捲繞軟式高分子基材固態電解質之二次電池結構及其製備方法 - Google Patents

可捲繞軟式高分子基材固態電解質之二次電池結構及其製備方法 Download PDF

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TWI738280B
TWI738280B TW109111256A TW109111256A TWI738280B TW I738280 B TWI738280 B TW I738280B TW 109111256 A TW109111256 A TW 109111256A TW 109111256 A TW109111256 A TW 109111256A TW I738280 B TWI738280 B TW I738280B
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solid electrolyte
secondary battery
electrode layer
cloth
based metal
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洪飛義
戴榮吉
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康那香企業股份有限公司
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Abstract

本發明有關於一種可捲繞軟式高分子基材固態電解質之二次電池結構及其製備方法，所述方法包括將一正極層鍍於一布質固態電解質之一側；再將一負極層鍍於布質固態電解質之另一側；以及進行一熱處理程序，使正極層與布質固態電解質之間形成一第一碳化層，而負極層與布質固態電解質之間形成一第二碳化層；藉此，本發明之二次電池結構可被捲繞以供使用。

Description

可捲繞軟式高分子基材固態電解質之二次電池結構及其製備方法
本發明係有關於一種二次電池結構及其製備方法，尤其係指一種可捲繞且具軟式高分子基材固態電解質的二次電池結構及其製備方法。
二次電池(Secondary Battery)又稱二級電池、蓄電池或可充電電池，目前全世界使用的二次電池大多為電解液的鋰電池，然而使用電解液的鋰電池有洩漏危害健康及環境與爆炸的疑慮，因此近年來已有業者開發以固態電解質取代電解液的固態電池。
舉例而言，中華民國專利公告第TWI617067B號即揭示一種固態富鎂型鹽質導電離子材料與製造方法，所述方法包括準備一金屬鎂(如純鎂、氧化鎂或鎂合金)，以及將金屬鎂混合於一酸類溶液中，並於溫度25℃-65℃作用1-12小時，以形成固態富鎂型鹽質導電離子材料，所述固態離子材料經正極與負極貼覆後形成正極/固態離子材料/負極，即成為全固態二次電池；上述採用鎂固態電解質取代電解液，不僅能有效提升電池效能與壽命，亦可解決電解液外漏安全問題。
然而，目前固態電解質電池大多仍處於研發階段而且無法捲繞，為解決此問題，已有相關業者進一步開發可彎折的電池。例如中國專利公開第CN110085904A號揭示「柔性複合固態電解質，全固態鋰離子電池及其製備方法」，所述柔性複合固態電解質主要由硫化物固態電解質及其改性物(具有毒性)、熱塑性聚合物及其改性物和鋰鹽製備而得，包含所述柔性複合固態電解質的柔性全固態電池具有良好的機械性能和彎折性、高循環穩定性和能量密度。
中國專利公開第CN109786817A號提出「固態鋰電池及其應用和製備無紡布增強的固態電解質膜的方法」，所述固態鋰電池，其包括無紡布增強的固態電解質膜、正極、尼龍和緩衝層，所述無紡布增強的固態電解質膜包括第一固態硫化物電解質(具有毒性)、無紡布和第一粘合劑；藉此，可解決固態鋰電池在組裝期間易發生短路、無法大量工業化生產、機械強度低等問題。
由於目前市場對於二次電池的需求量極大，因此如何開發出各種具固態電解質的二次電池，並提升其電容量與充放電效率，仍是相關領域發明人思及之方向。
今，發明人即是鑑於上述現有之二次電池於實際實施使用時仍具有多處缺失，於是藉由其豐富專業知識及多年之實務經驗所輔佐，而加以改善，並據此研創出本發明。
本發明主要目的為提供一種可捲繞軟式高分子基材固態電解質之二次電池結構及其製備方法，其藉由不織布技術使固態電解質之二次電池可以彎折和捲繞。
為了達到上述實施目的，本發明提供一種可捲繞軟式高分子基材固態電解質之二次電池的製備方法，係包含有步驟一：將一正極層鍍於一布質固態電解質之一側；步驟二：將一負極層鍍於布質固態電解質之另一側；以及步驟三：進行一熱處理程序，使正極層與布質固態電解質之間形成一第一碳化層，而負極層與布質固態電解質之間形成一第二碳化層，其中熱處理程序為紅外線處理或微波處理，且係於溫度80℃~150℃之環境下持續30秒~300秒。
本發明亦提供一種可捲繞軟式高分子基材固態電解質之二次電池結構，係依序具有一正極層、一第一碳化層、一布質固態電解質、一第二碳化層與一負極層。
於本發明之一實施例中，正極層為鎂基金屬、鋰基金屬、鈉基金屬、鎵基金屬、錫基金屬或合金金屬箔片，負極層為碳膜、金屬膜或合金膜。
於本發明之一實施例中，布質固態電解質為不織布或棉布，而不織布選用聚丙烯(PP)、聚乙烯(PE)、聚對苯二甲酸乙二酯(PET)或尼龍材料。
於本發明之一實施例中，第一碳化層與第二碳化層係為金屬碳化物，可例如為碳化鎂(MgC)、碳化鋰(LiC)、碳化鈉(NaC)、碳化鎵(GaC)、碳化錫(SnC)。
藉此，本發明全固態二次電池可解決現有二次電池因使用電解液而有可能洩漏與爆炸的缺失，並且本案藉由不織布技術製得的固態電解質(無毒性)，讓二次電池可以彎折和捲繞，並達到耐高溫、可快速充放電功效。
本發明之目的及其結構功能上的優點，將依據以下圖面所示之結構，配合具體實施例予以說明，俾使審查委員能對本發明有更深入且具體之瞭解。
本發明提供一種可捲繞軟式高分子基材固態電解質之二次電池結構，其包含有步驟一：將一正極層鍍於一布質固態電解質之一側；步驟二：將一負極層鍍於布質固態電解質之另一側；以及步驟三：進行一熱處理程序，使正極層與布質固態電解質之間形成一第一碳化層，而負極層與布質固態電解質之間形成一第二碳化層；較佳而言，所述熱處理程序可例如為紅外線處理或微波處理，於較適和溫度約80℃~150℃之環境下持續30秒~300秒。
再者，本發明亦提供一種可捲繞軟式高分子基材固態電解質之二次電池結構，係依序具有一正極層、一第一碳化層、一布質固態電解質、一第二碳化層與一負極層。
較佳而言，上述正極層可例如為鎂基金屬、鋰基金屬、鈉基金屬、鎵基金屬、錫基金屬或合金金屬箔片；負極層可例如為碳膜、金屬膜或合金膜；所述布質固態電解質可選自不織布或棉布，而不織布選用聚丙烯(PP)、聚乙烯(PE)、聚對苯二甲酸乙二酯(PET)或尼龍材料；所述第一碳化層與第二碳化層為金屬碳化物，可例如為碳化鎂(MgC)、碳化鋰(LiC)、碳化鈉(NaC)、碳化鎵(GaC)、碳化錫(SnC)。
此外，藉由下述具體實施例，可進一步證明本發明可實際應用之範圍，但不意欲以任何形式限制本發明之範圍。
實施例一：製備可捲繞軟式高分子基材固態電解質之二次電池結構
請參閱第一圖，為本發明其較佳實施例之二次電池經熱處理程序示意圖，即是具雙邊鍍層之布質二次電池的製備方法，其具有充放電特性，製備方法包含有：將負極層(5) (碳膜、金屬膜或合金膜等)鍍於一布質固態電解質(3)上，而在布質固態電解質的另一側則鍍上正極層(1) (鎂基、鋰基、鈉基、鎵基、錫基或合金金屬箔片等)；布質固態電解質之基材材料可為不織布或棉布，若使用不織布，則選用聚丙烯(PP)、聚乙烯(PE)、聚對苯二甲酸乙二酯(PET)或尼龍材料；以及進行一熱處理程序，熱處理程序係使用紅外線處理或微波處理，並於溫度80℃~150℃之環境下進行30秒~300秒，使負極層(5)與布質固態電解質(3)之界面以及正極層(1)與布質固態電解質(3)之界面各形成一碳化層(2)(4)，該碳化層(2)(4)係為碳化鎂(MgC)、碳化鋰(LiC)、或金屬碳化物等可使具布質固態電解質之二次電池具有高溫電池應用特性。
藉此，本發明具固態電解質之二次電池結構，其包含有正極層(1)、布質固態電解質(3)與負極層(5)，且又有兩層碳化層(2)(4)分別形成於正極層(1)與布質固態電解質(3)之間以及負極層(5)與布質固態電解質(3)之間；正極層(1)係使用鎂(Mg)、鋰(Li)化合物、鈉(Na)化合物、鎵(Ga)化合物、錫(Sn)化合物或合金金屬箔片，其藉助濺鍍、噴鍍、蒸鍍或粉刷等方式形成；負極層(5)則使用碳(C)膜、金屬膜或合金膜，其利用濺鍍、噴鍍、蒸鍍或粉刷等方式形成；布質固態電解質(3)使用不織布或棉布材料，若為不織布則選用聚丙烯(PP)、聚乙烯(PE)、聚對苯二甲酸乙二酯(PET)或尼龍材料，此布質固態電解質(3)可執行彎折、捲繞或堆疊等動作。
實施例二：性能測試
各式固態電池: 正極/布質固態電解質(代稱B)/碳極在各溫度條件之平均充放克電容量 (充電:12V-1h, 充放次數:100)的測試結果請參表一。
表一
mAh/g 鋰/B/碳 鎂/B/碳 鈉/B/碳
-150 C 961 885 1024
室溫 822 638 861
550 C 348 549 783
850 C 262 312 400
各式固態電池: 鎂正極/布質固態電解質(代稱B)/負極在各溫度條件之平均充放克電容量 (充電:12V-1h, 充放次數:100)的測試結果請參表二。
表二
mAh/g 鎂/B/碳 鎂/B/鎵 鎂/B/錫
-150 C 885 1110 1008
室溫 638 1186 876
550 C 549 878 772
850 C 312 710 609
由上述之實施說明可知，本發明與現有技術相較之下，本發明具有以下優點：
1.本發明採用高分子基材固態電解質，因此無使用電解液，可避免電解液滲漏而危害健康及環境。
2.本發明電池結構均採用環保安全材料，且鎂為鹼土金屬，其價電子數為2，與價電子數為1的鋰相比，可提供近兩倍電量，再加上鎂不會生成枝晶，電池不會有爆炸風險。
3.本發明可達到耐高溫、高電容量與快速充放電功效。
4.本發明採用布質固態電解質，因此二次電池成品可以彎折和捲繞。
綜上所述，本發明之可捲繞軟式高分子基材固態電解質之二次電池結構及其製備方法，的確能藉由上述所揭露之實施例，達到所預期之使用功效，且本發明亦未曾公開於申請前，誠已完全符合專利法之規定與要求。爰依法提出發明專利之申請，懇請惠予審查，並賜准專利，則實感德便。
惟，上述所揭之圖示及說明，僅為本發明之較佳實施例，非為限定本發明之保護範圍；大凡熟悉該項技藝之人士，其所依本發明之特徵範疇，所作之其它等效變化或修飾，皆應視為不脫離本發明之設計範疇。
1:正極層
2:碳化層
3:布質固態電解質
4:碳化層
5:負極層
第一圖：本發明其較佳實施例之二次電池經熱處理程序示意圖。
1:正極層
2:碳化層
3:布質固態電解質
4:碳化層
5:負極層

Claims (8)

  1. 一種可捲繞軟式高分子基材固態電解質之二次電池的製備方法，係包含有：步驟一：將一正極層鍍於一布質固態電解質之一側；步驟二：將一負極層鍍於該布質固態電解質之另一側；以及步驟三：進行一熱處理程序，使該正極層與該布質固態電解質之間形成一第一碳化層，而該負極層與該布質固態電解質之間形成一第二碳化層，其中該熱處理程序為紅外線處理或微波處理，且係於溫度80℃~150℃之環境下持續30秒~300秒。
  2. 如請求項1所述可捲繞軟式高分子基材固態電解質之二次電池的製備方法，其中該正極層為鎂基金屬、鋰基金屬、鈉基金屬、鎵基金屬、錫基金屬或合金金屬箔片。
  3. 如請求項1所述可捲繞軟式高分子基材固態電解質之二次電池的製備方法，其中該負極層為碳膜、金屬膜或合金膜。
  4. 如請求項1所述可捲繞軟式高分子基材固態電解質之二次電池的製備方法，其中該布質固態電解質為不織布或棉布，而該不織布選用聚丙烯(PP)、聚乙烯(PE)、聚對苯二甲酸乙二酯(PET)或尼龍材料。
  5. 如請求項1所述可捲繞軟式高分子基材固態電解質之二次電池的製備方法，其中該第一碳化層與該第二碳化層係為金屬碳化物。
  6. 一種可捲繞軟式高分子基材固態電解質之二次電池結構，係依序具有一正極層、一第一碳化層、一布質固態電解質、一第二碳化層與一負極層，其中該第一碳化層與該第二碳化層係為金屬碳化物。
  7. 如請求項6所述可捲繞軟式高分子基材固態電解質之二次電池結構，其中該正極層為鎂基金屬、鋰基金屬、鈉基金屬、鎵基金屬、錫基金屬或合金金屬箔片；該負極層為碳膜、金屬膜或合金膜。
  8. 如請求項6所述可捲繞軟式高分子基材固態電解質之二次電池結構，其中該布質固態電解質為不織布或棉布，而該不織布選用聚丙烯(PP)、聚乙烯(PE)、聚對苯二甲酸乙二酯(PET)或尼龍材料。
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