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/ 博客文章 / 電池知識 / 鋰電池的發展 電池裝置的起源可能要從萊頓瓶的發現開始。 萊頓瓶最早由荷蘭科學家 Pieter van Musschenbroek 於 1745 年發明。萊頓瓶是一種原始的電容器裝置。 它由兩片由絕緣體隔開的金屬片組成。 上面的金屬棒是用來儲存和釋放電荷的。 當你觸碰金屬球時,萊頓瓶可以保持或除去內部電能,其原理和製備很簡單。 有興趣的人可以自己在家製作,但由於製作方法簡單,自放電現像比較嚴重。 一般情況下,幾小時到幾天內就會將電量全部放完。 然而,萊頓瓶的出現標誌著電的研究進入了一個新階段。
1790年代,義大利科學家Luigi Galvani發現用鋅線和銅線連接青蛙腿,發現青蛙腿會抽動,於是提出了「生物電」的概念。 這項發現讓義大利科學家亞歷山德羅全身抽搐。 沃爾塔反對,沃爾塔認為青蛙腿的抽動來自於金屬產生的電流而不是青蛙身上的電流。 為了反駁伽伐尼的理論,伏打提出了他著名的伏打堆疊。 伏打電池組由鋅片和銅片組成,中間夾有浸泡在鹽水中的紙板。 這是所提出的化學電池的原型。
伏打電池的電極反應方程式:
正極:2H^++2e^-→H_2
負極:Zn→〖Zn〗^(2+)+2e^-
1836年,英國科學家約翰·弗雷德里克·丹尼爾發明了丹尼爾電池,解決了電池中存在氣泡的問題。 丹尼爾電池具有現代化學電池的主要形式。 它由兩個部分組成。 將正極部分浸入硫酸銅溶液中。 銅的另一部分是浸在硫酸鋅溶液中的鋅。 最初的丹尼爾電池在銅罐中裝滿硫酸銅溶液,並在中心插入陶瓷多孔圓柱形容器。 在這個陶瓷容器中,有一根鋅棒和硫酸鋅作為負極。 在解決方案中,陶瓷容器中的小孔允許兩個鍵交換離子。 現代丹尼爾電池大多採用鹽橋或半透膜來達到這種效果。 丹尼爾電池曾被用作電報網路的電源,直到乾電池取代它們。
丹尼爾電池的電極反應方程式:
正極:〖Cu〗^(2+)+2e^-→Cu
負極:Zn→〖Zn〗^(2+)+2e^-
至此,電池的主要形狀已確定,包括正極、負極和電解液。 正是在這樣的基礎上,電池在接下來的100年裡得到了快速的發展。 許多新的電池系統出現,其中包括法國科學家加斯頓·普蘭特(Gaston Planté) 在1856 年發明了鉛酸電池。鉛酸電池以其大的輸出電流和低廉的價格引起了廣泛的關注,因此被應用於許多移動設備中,例如早期的電動車等。汽車。 常被用作一些醫院和基地台的備用電源。 鉛酸電池主要由鉛、二氧化鉛和硫酸溶液組成,其電壓可達2V左右。 即使到了現代,鉛酸電池由於技術成熟、價格低廉、水系系統更安全等原因也沒有被淘汰。
鉛酸蓄電池的電極反應方程式:
Positive electrode: PbO_2+〖SO〗_4^(2-)+4H^++2e^-→Pb〖SO〗_4+2H_2 O
負極:Pb+〖SO〗_4^(2-)→Pb〖SO〗_4+2e^-
鎳鎘電池由瑞典科學家Waldemar Jungner於1899年發明,由於其能量密度比鉛酸電池更高,因此更廣泛地應用於小型行動電子設備,例如早期的隨身聽。 與鉛酸電池類似。 鎳鎘電池自1990年代以來也被廣泛使用,但其毒性相對較高,且電池本身俱有特定的記憶效應。 這就是為什麼我們經常聽到一些老年人說電池必須完全放電後充電,廢電池會污染土地等等。 (注意,即使現在的電池毒性很大,也不應該隨處丟棄,但是現在的鋰電池沒有記憶好處,過度放電對電池壽命有害。)鎳鎘電池對環境的破壞更大,而且它們的內阻會隨溫度變化,充電時可能會因電流過大而損壞。 鎳氫電池在2005年左右逐漸淘汰,至今市場上很少見到鎳鎘電池。
鎳鎘電池電極反應方程式:
Positive electrode: 2NiO(OH)+2H_2 O+2e^-→2OH^-+2Ni〖(OH)〗_2
負極:Cd+2OH^-→Cd〖(OH)〗_2+2e^-
鋰金屬電池級
1960年代,人們終於正式進入鋰電池時代。
鋰金屬本身於1817年被發現,人們很快就意識到鋰金屬的物理和化學特性本質上可以用作電池材料。 它具有低密度(0.534g 〖cm〗^(-3))、大容量(理論高達3860mAh g^(-1))和低電位(與標準氫電極相比-3.04V)。 這些幾乎都在告訴人們我是理想電池的負極材料。 然而,鋰金屬本身存在著巨大的問題。 過於活潑,與水發生劇烈反應,對操作環境要求較高。 因此,長期以來,人們對此束手無策。
1913年,路易斯和凱斯測量了鋰金屬電極的電位。 並用丙胺溶液中的碘化鋰作為電解液進行了電池測試,雖然失敗了。
1958年,William Sidney Harris在他的博士論文中提到,他將鋰金屬放入不同的有機酯溶液中,並觀察到一系列鈍化層的形成(包括高氯酸中的鋰金屬)。 鋰LiClO_4
碳酸丙烯酯的PC溶液中的現象,而該溶液是未來鋰電池中至關重要的電解質系統),並且觀察到了特定的離子傳輸現象,因此在此基礎上做了一些初步的電沉積實驗。 這些實驗正式導致了鋰電池的發展。
1965年,NASA對Li||Cu電池在高氯酸鋰PC溶液中的充放電現象進行了深入研究。 其他電解質體系,包括LiBF_4、LiI、LiAl〖Cl〗_4、LiCl的分析,這項研究引起了人們對有機電解質體系的極大興趣。
1969年,一項專利顯示,有人開始嘗試將使用鋰、鈉和鉀金屬的有機溶液電池商業化。
1970年,日本松下公司發明了Li‖CF_x┤電池,其中x的比值一般為0.5-1。 CF_x是碳氟化合物。 氟氣雖然有劇毒,但碳氟化合物本身是灰白色無毒粉末。 Li‖CF_x┤電池的出現可以說是第一個真正商業化的鋰電池。 Li‖CF_x┤電池是一次電池。 不過它的容量還是很大的,理論容量為865mAh〖Kg〗^(-1),且在長距離放電電壓非常穩定。 因此,功率穩定,自放電現像小。 但其速率性能很差,無法充電。 因此一般與二氧化錳複合製成Li‖CF_x┤-MnO_2電池,用作一些小型感測器、鐘錶等的內部電池,至今尚未被淘汰。
正極:CF_x+xe^-+x〖Li〗^+→C+xLiF
負極:Li→〖Li〗^++e^-
1975年,日本三洋公司發明了Li‖MnO_2┤電池,首先用於可充電太陽能計算器。 這可以算是第一支可充電鋰電池。 雖然這款產品當時在日本取得了巨大成功,但人們對這種材料並沒有深入的了解,也不知道它的鋰和二氧化錳。 這種反應背後的原因是什麼?
幾乎在同一時間,美國人正在尋找一種可重複使用的電池,我們現在稱之為二次電池。
1972年,MBAArmand(一些科學家的名字一開始沒有翻譯)在會議論文中提出了M_(0.5) Fe〖(CN)〗_3(其中M為鹼金屬)等具有普魯士藍結構的材料。 ,並研究了其離子嵌入現象。 1973年,貝爾實驗室的J. Broadhead等人研究了金屬二硫屬化物中硫原子和碘原子的插層現象。 這些對離子嵌入現象的初步研究是鋰電池逐步進步的最重要的驅動力。 最初的研究是精確的,因為這些研究使得後來的鋰離子電池成為可能。
1975年,埃克森公司(埃克森美孚的前身)的Martin B. Dines對一系列過渡金屬二硫化物與鹼金屬之間的插層進行了初步計算和實驗,同年,埃克森公司的另一位科學家MS Whittingham發表了一項專利在 Li‖TiS_2 ┤ 池上。 並且在1977年,Exoon將基於Li-Al‖TiS_2┤的電池商業化,其中鋰鋁合金可以增強電池的安全性(儘管仍然存在更顯著的風險)。 此後,此類電池系統已陸續被美國Eveready公司採用。 電池公司和格雷斯公司的商業化。 Li‖TiS_2┤電池可以說是第一個真正意義上的二次鋰電池,也是當時最熱門的電池系統。 當時其能量密度約為鉛酸電池的2-3倍。
正極:TiS_2+xe^-+x〖Li〗^+→〖Li〗_x TiS_2
負極:Li→〖Li〗^++e^-
同時,加拿大科學家MA Py於2年發明了Li‖MoS_1983┤電池,在60/65C時能量密度可達1-1Wh〖Kg〗^(-3),相當於Li‖TiS_2┤電池。 基於此,1987年,加拿大莫利能源公司推出了真正廣泛商業化的鋰電池,受到全球廣泛的追捧。 這本來應該是一個具有歷史意義的事件,但諷刺的是,這也導致了莫里後來的衰落。 1989年春,摩力公司推出了第二代Li‖MoS_2┤電池產品。 1989年春末,摩力第一代Li‖MoS_2┤電池產品爆炸,造成大規模恐慌。 同年夏天,所有產品被召回,並對受害者進行了賠償。 同年底,Moli Energy宣布破產,並於1990年春天被日本NEC收購。值得一提的是,據傳當時的加拿大科學家Jeff Dahn正在領導Moli的電池項目因反對Li‖MoS_2┤電池繼續上市而辭職。
正極:MoS_2+xe^-+x〖Li〗^+→〖Li〗_x MoS_2
負極:Li→〖Li〗^++e^-
至此,鋰金屬電池已逐漸淡出大眾的視線。 我們可以看到,1970年到1980年期間,科學家對鋰電池的研究主要集中在正極材料上。 最終目標始終集中在過渡金屬二硫屬化物。 由於它們的層狀結構(過渡金屬二硫屬化物現在作為二維材料被廣泛研究),它們的層和層之間有足夠的間隙來容納鋰離子的插入。 當時這時期負極材料的研究太少了。 儘管一些研究集中在鋰金屬的合金化以增強其穩定性,但鋰金屬本身太不穩定且危險。 雖然莫力電池爆炸是一件震驚世界的事件,但鋰金屬電池爆炸的案例已經發生過很多起。
而且,人們對鋰電池爆炸的原因也不是很了解。 此外,金屬鋰因其良好的性能一度被認為是不可取代的負極材料。 莫力電池爆炸後,人們對鋰金屬電池的接受度直線下降,鋰電池進入黑暗期。
為了擁有更安全的電池,人們必須從有害的電極材料開始。 儘管如此,這裡仍然存在一系列問題:鋰金屬的電位較淺,使用其他複合負極會增加負極電位,這樣,鋰電池的整體電位差就會減小,從而降低風暴的能量密度。 因此,科學家必須尋找相應的高壓正極材料。 同時,電池的電解液必須配合正負極電壓和循環穩定性。 同時電解液的導電性和耐熱性較好。 這一系列問題困擾了科學家很長一段時間,以期找到更滿意的答案。
科學家首先要解決的問題是找到一種安全、無害、可以取代鋰金屬的電極材料。 金屬鋰本身化學活性太大,出現一系列枝晶生長問題,對使用環境和條件過於苛刻,並不安全。 石墨現在是鋰離子電池負極的主體,早在1976年就開始研究其在鋰電池中的應用。1976年,Besenhard,JO對LiC_R的電化學合成進行了較為詳細的研究。 然而,雖然石墨具有優異的性能(高導電性、高容量、低電位、惰性等),但當時鋰電池所使用的電解液一般是上述LiClO_4的PC溶液。 石墨有一個重大問題。 在沒有保護的情況下,電解液PC分子也會隨著鋰離子嵌入進入石墨結構,導致循環性能下降。 因此,石墨並沒有受到當時科學家的青睞。
至於正極材料,經過鋰金屬電池階段的研究,科學家發現鋰化負極材料本身也是一種可逆性良好的儲鋰材料,如LiTiS_2,〖Li〗_x V〖Se〗_2 (x =1,2)等,並在此基礎上開發了〖Li〗_x V_2 O_5(0.35≤x<3)、LiV_2 O_8等材料。 科學家也逐漸熟悉了各種一維離子通道(1D)、二維層狀離子插層(1D)和2維離子傳輸網狀結構。
John B. Goodenough教授最著名的LiCoO_2(LCO)研究也發生在此時。 1979 年,Goodenougd 等人。 2年受到一篇關於NaCoO_1973結構的文章的啟發,發現了LCO並發表了專利文章。 LCO具有類似過渡金屬二硫化物的層狀插層結構,其中鋰離子可以可逆地嵌入和脫嵌。 如果鋰離子完全脫出,就會形成CoO_2的密排結構,可以重新嵌入鋰離子來獲得鋰(當然,實際電池不會讓鋰離子完全脫出,這會導致容量快速衰減)。 1986年,當時還在日本旭化成公司工作的吉野彰首次將LCO、焦炭、LiClO_4 PC方案三者結合起來,成為第一個現代鋰離子二次電池,成為當前鋰離子二次電池的基石。電池。 索尼很快就注意到了這位「足夠好」老人的LCO專利,並獲得了使用授權。 1991年,LCO鋰離子電池商業化。 鋰離子電池的概念也在此時出現,其理念也延續至今。 (值得注意的是,索尼第一代鋰離子電池和吉野彰也使用硬碳作為負極而不是石墨,原因是上面的PC有石墨插層)
正極:6C+xe^-+x〖Li〗^+→〖Li〗_x C_6
負極:LiCoO_2→〖Li〗_(1-x) CoO_2+x〖Li〗^++xe^-
另一方面,1978年,Armand, M.提出採用聚乙二醇(PEO)作為固體聚合物電解質,以解決上述石墨負極易嵌入溶劑PC分子的問題(當時的主流電解質仍為聚乙二醇)。採用PC、DEC混合溶液),首次將石墨放入鋰電池系統中,並於次年提出了搖椅電池(rocking-chair)的概念。 這樣的觀念一直延續至今。 目前主流的電解液體系,如ED/DEC、EC/DMC等,在1990年代慢慢出現,並沿用至今。
在同一時期,科學家也探索了一系列電池:Li‖Nb〖Se〗_3┤電池、Li‖V〖SE〗_2┤電池、Li‖〖Ag〗_2 V_4┤O_11電池、Li‖CuO┤電池、 Li ‖ I_2 ┤電池等,因為現在比較不值錢,研究的種類不多所以就不詳細介紹了。
1991年後的鋰離子電池發展時代,就是我們現在所處的時代。這裡我不會詳細總結發展過程,只是簡單介紹幾種鋰離子電池的化學體系。
目前的鋰離子電池系統的介紹,這裡是下一部分。