TW202419637A - 鋰離子二次電池的負極材料及其負極、電池及製備方法 - Google Patents
鋰離子二次電池的負極材料及其負極、電池及製備方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000010405 anode material Substances 0.000 title abstract 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007773 negative electrode material Substances 0.000 claims description 39
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- -1 fluorocarbon compound Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 239000007784 solid electrolyte Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001947 lithium oxide Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Abstract
一種鋰離子二次電池的負極材料,包含鈦酸鋰以及包覆在該鈦酸鋰之表面的改質層,其中該改質層為碳氟化合物,該鋰離子二次電池的負極材料於鈦酸鋰表面形成C-F鍵結的表面修飾,能夠用於鋰電子二次電池,使用該負極材料製作鋰電子二次電池,能夠在避免電極表面形成固態電解質層的同時,得到良好的導電性及避免產氣的問題。
Description
本發明係關於鋰離子二次電池的負極材料及其該負極材料製備方法,以及使用該負極材料的負極及鋰離子二次電池,特別是一種於鈦酸鋰表面包覆有碳氟化合物改質層的鋰離子二次電池的負極材料。
隨著可攜式電子裝置、無線通訊及電動運輸載具等科技之發展,俗稱可充電電池的「鋰離子二次電池」的使用量日漸增加,對其穩定性的要求也逐漸提高。
鋰離子電池負極主流材料為石墨,但由於其工作電壓低,電池在過度充電與快速充電的狀態下,容易在石墨表面析出枝晶狀的鋰金屬(lithium dendrite),而此鋰枝晶經過不斷成長,可能會將正負極之間的隔離膜刺穿,造成熱失控、燃燒甚至***等安全性疑慮。
對應於此問題,目前作為鋰電池負極材料,能夠使用鈦酸鋰金屬,鈦酸鋰作為鋰離子電池負極材料具有以下的特性:(1)鈦酸鋰電池在充放電過程中,鋰離子的嵌入及脫出所造成的結構影響極低,並且伴隨良好的循環穩定性;(2)鈦酸鋰電池工作電壓約為1.55V,高於傳統石墨負極之工作電壓,在充放電過程中,不易形成固態電解質層(Solid Electrolyte Interface, SEI)及鋰枝晶,安全性高。
但是與此同時,鈦酸鋰電池在使用上亦有其限制,由於鈦酸鋰的鈦價數為+4,使鈦酸鋰的導電性降低,在高倍率的效能不盡理想,又由於鈦酸鋰放電過程中不易形成固態電解質層,因此相對的在電化學反應中,鈦酸鋰經常會與電解液直接接觸,導致副反應產生以至於有產氣的問題。
因此,本發明的目的在於藉由對鈦酸鋰進行表面處理,以解決鈦酸鋰的導電度及產氣的問題。
本發明為解決習知技術之問題所採用之技術手段係提供一種鋰離子二次電池的負極材料,包含:鈦酸鋰;以及改質層,包覆在該鈦酸鋰之表面,其中該改質層為碳氟化合物。
在本發明的一實施例中係提供一種鋰離子二次電池的負極,其特徵在於包含如上所述的鋰離子二次電池的負極材料。
在本發明的一實施例中係提供一種鋰離子二次電池的負極,其中該鋰離子二次電池的負極係藉由將上述鋰離子二次電池的負極材料與導電碳及黏著劑混合並塗佈於鋁箔上所形成。
在本發明的一實施例中係提供一種鋰離子二次電池的負極,其中該鋰離子二次電池的負極材料之含量為90重量百分比,該導電碳之含量為5重量百分比,該黏著劑之含量為5重量百分比。
在本發明的一實施例中係提供一種鋰離子二次電池,其特徵在於包含如上所述的鋰離子二次電池的負極。
在本發明的一實施例中係提供一種鋰離子二次電池,其中該鋰離子二次電池係為鋰離子鈕扣型電池。
在本發明的一實施例中係提供一種鋰離子二次電池,其中該鋰離子二次電池之正極係選自鈷酸鋰、鎳酸鋰、錳酸鋰、三元正極、磷酸鋰鐵、磷酸鋰鐵錳、及三元正極與磷酸鋰鐵錳結合而成的複合正極所構成的群組。
在本發明的一實施例中係提供一種鋰離子二次電池的負極材料的製備方法,係用於製備如上所述的鋰離子二次電池的負極材料,該製備方法包含下列步驟:將鈦酸鋰的粉末及聚偏二氟乙烯的粉末混合後,進行燒結,而得到表面包覆有碳氟化合物之改質層的鈦酸鋰,作為該鋰離子二次電池的負極材料。
在本發明的一實施例中係提供一種鋰離子二次電池的負極材料的製備方法,其中在混合時,該鈦酸鋰的粉末的含量為99重量百分比,該聚偏二氟乙烯的粉末之含量為1重量百分比。
在本發明的一實施例中係提供一種鋰離子二次電池的負極材料的製備方法,其中燒結為在空氣下以300°C進行2小時。
經由本發明所採用之技術手段,能夠得到一種於鈦酸鋰表面形成碳氟鍵的表面修飾,能夠用於鋰電子二次電池的負極材料,使用該負極材料製作鋰電子二次電池,能夠在避免電極表面形成固態電解質層的同時,得到良好的導電性及避免產氣的問題。
以下根據第1圖至第5圖,而說明本發明的實施方式。該說明並非為限制本發明的實施方式,而為本發明之實施例的一種。
依據本發明的一實施例的鋰離子二次電池的負極材料,包含鈦酸鋰,以及包覆在該鈦酸鋰之表面的改質層,其中該改質層為碳氟化合物。
本發明係於鈦酸鋰的表面形成含碳氟鍵的改質層,當受熱時會產生如以下化學式1的反應,含碳氟鍵的改質層中的分子分解形成碳-碳雙鍵及碳-氟鍵,其中碳-氟鍵中氟電負度較大,將造成碳-氟鍵中部分帶負電的狀況。
【化學式1】
上述式中的碳-氟鍵有利於提升離子導電度,並且藉由塗覆於鈦酸鋰表面能夠抑制鈦酸鋰的表面在高溫下與電解質產生副反應而產氣。
依據本發明的一實施例的鋰離子二次電池的負極,其中該鋰離子二次電池的負極係藉由將上述鋰離子二次電池的負極材料與導電碳及黏著劑混合並塗佈於鋁箔上所形成。
依據本發明的一實施例的鋰離子二次電池的負極,其中該鋰離子二次電池的負極材料之含量為90重量百分比,該導電碳之含量為5重量百分比,該黏著劑之含量為5重量百分比。
依據本發明的一實施例的鋰離子二次電池,其特徵在於包含如上所述的鋰離子二次電池的負極。
依據本發明的一實施例的鋰離子二次電池,其中該鋰離子二次電池係為鋰離子鈕扣型電池。
依據本發明的一實施例的鋰離子二次電池,其中該鋰離子二次電池之正極的材料係選自鈷酸鋰、鎳酸鋰、錳酸鋰、三元正極材料、磷酸鋰鐵、磷酸鋰鐵錳、及三元正極材料與磷酸鋰鐵錳結合而成的複合正極材料所構成的群組。
依據本發明的一實施例的鋰離子二次電池的負極材料的製備方法,係用於製備如上所述的鋰離子二次電池的負極材料,該製備方法包含下列步驟:將鈦酸鋰的粉末及聚偏二氟乙烯的粉末混合後,進行燒結,而得到表面包覆有碳氟化合物之改質層的鈦酸鋰,作為該鋰離子二次電池的負極材料。
依據本發明的一實施例的鋰離子二次電池的負極材料的製備方法,其中在混合時,該鈦酸鋰的粉末的含量為99重量百分比,該聚偏二氟乙烯的粉末之含量為1重量百分比。
依據本發明的一實施例的鋰離子二次電池的負極材料的製備方法,其中燒結為在空氣下以300°C進行2小時。
本實施例中將該負極材料:作為黏著劑的聚偏二氟乙烯(polyvinylidene difluoride,PVDF):作為導電碳的Super P的重量百分比的比為90:5:5,再加入適當份量的N-甲基吡咯烷酮(N-Methylpyrrolidone,NMP)溶劑,混合攪拌8小時形成均勻稠狀漿料,接著將混合好的漿料塗在電池用鋁箔,送入烘箱烘乾,再將乾燥後的負極極片裁切為9.5mm的圓形極片,最後以攝氏110°C真空乾燥12小時,送入手套箱備用。
於手套箱中,以鋰金屬當作對電極,進行鋰金屬、隔離膜、加入添加劑之電解液及如上述實施例製成的極片的鈕扣型半電池的組裝,並以此半電池進行後述的電性測試。
該電解液包含電解質及非水性溶劑,其中電解質使用六氟磷酸鋰(LiPF
6),非水溶性溶液選用碳酸乙烯酯(ethylene carbonates, EC)及碳酸二甲酯(dimethyl carbonate, DMC),使1.2M的LiPF
6溶於EC與DMC的混合溶劑,EC與DMC的混合溶劑的比例為EC/DMC=3/7。
組裝的鈕扣型電池作為實驗組的B組,並取電極片為未經處理的鈦酸鋰的鈕扣型電池作為對照組的A組。
首先進行首圈充放電及極化現象測試,測試時以1C放電倍率進行充放放電,其結果的曲線圖顯示於圖1,而實驗結果數值顯示於表1。
【表1】
實驗 | 首圈放電之電容量(mAh/g) | 首圈放電之庫倫效率(%) | 平台間電壓差(V) |
A組 | 166.98 | 89.57 | 0.198 |
B組 | 172.08 | 95.59 | 0.101 |
如圖1的結果曲線圖及表1所示,B組經過測定其首圈電容量的172.08 mAh/g明顯高於B組的166.98 mAh/g,另一方面,圖中的各組的二個平台之間的電壓差則是顯示該電池中的極化現象的程度,如表1所示B組之極化現象明顯小於A組。
由上述結果可知,表面氟化的鈦酸鋰能夠有效提升電容量,且因外層離子導電層的影響而極化現象明顯減小。
接著進行鈕扣型電池的循環壽命測試,測試時以1C進行充放放電,共100循環,其結果的曲線圖顯示於圖2,而實驗結果數值顯示於表2。
【表2】
實驗 | 起始電容量(mAh/g) | 起始庫倫效率(%) | 最終電容量(mAh/g) | 電容保持率(%) |
A組 | 166.98 | 89.57 | 129.83 | 84.04 |
B組 | 172.08 | 95.59 | 152.99 | 93.07 |
如圖2及表2所示,B組經過100循環的1C充放放電,起始電容量及最終電容量皆高於A組,而電容量的變化亦小於A組。
由此可知,表面氟化的鈦酸鋰電池相較於未經表面處理的鈦酸鋰電池具有較高的電容量及循環穩定性。
接著進行鈕扣型電池的倍率性能測試,測試時分別以0.2C、0.5C、1C、2C、5C及10C進行充放放電,每一倍率進行10循環,其結果的曲線圖顯示於圖3。
如圖3所示,即使在10C的高倍率下,B組的電容量(102.57 mAh/g)亦能夠維持大於60%的初始電容量(0.2C,162.01 mAh/g)。
由此可知,表面氟化的鈦酸鋰電池相較於未經表面處理的鈦酸鋰電池,有利於高倍率放電下的離子遷移。
接著進行鈕扣型電池的高溫倍率性能測試,測試時分別以1C及3C於65°C下進行充放放電,每一倍率進行100循環,其在3C下進行100循環的結果的曲線圖顯示於圖4,於1C下進行100循環的結果的曲線圖顯示於圖5。
如圖4及圖5所示,A組在高溫環境下,進行1C及3C的放電後電容量明顯下降,而B組在高溫環境下,在電流倍率1C時的電容保持率為92.15%,在電流倍率3C時的電容保持率為85.22%,與A組相比有明顯的改善。
由此可知,表面氟化的鈦酸鋰電池相較於未經表面處理的鈦酸鋰電池,即使在高溫環境,電解液易與電極表面產生反應的狀況下,表面氟化的鈦酸鋰的改質層依然能夠保護鈦酸鋰表面,抑制與電解液產生的副反應。
進一步,進行有將表面改質後的鈦酸鋰粉末進行掃描穿透式電子顯微鏡(scanning transmission electron microscope, STEM)的能量散射光譜儀分析(Energy Dispersive Spectrometer mapping, EDS-mapping)。
自分析結果能夠得知,自鈦酸鋰的表面得到碳元素及氟元素的訊號,可以明確得知鈦酸鋰的表面經碳氟化。
經由本發明所採用之技術手段,本發明的鋰離子二次電池的負極材料的製備方法所得到的鋰離子二次電池的負極材料,於鈦酸鋰表面形成C-F鍵結的表面修飾,能夠用於鋰電子二次電池,使用該負極材料製作鋰電子二次電池,能夠在避免電極表面形成固態電解質層的同時,得到良好的導電性及避免產氣的問題。
以上之敘述以及說明僅為本發明之較佳實施例之說明,對於此項技術具有通常知識者當可依據以下所界定申請專利範圍以及上述之說明而作其他之修改,惟此些修改仍應是為本發明之發明精神而在本發明之權利範圍中。
圖1係顯示根據本發明的一實施例中的鋰離子二次電池的充放電測試結果曲線圖。
圖2係顯示根據本發明的一實施例中的鋰離子二次電池的循環壽命測試結果曲線圖。
圖3係顯示根據本發明的一實施例中的鋰離子二次電池的倍率性能測試結果曲線圖。
圖4係顯示根據本發明的一實施例中的鋰離子二次電池的高溫倍率性能測試結果曲線圖。
圖5係顯示根據本發明的一實施例中的鋰離子二次電池的高溫倍率性能測試結果曲線圖。
Claims (10)
- 一種鋰離子二次電池的負極材料,包含: 鈦酸鋰;以及 改質層,包覆在該鈦酸鋰之表面,其中該改質層為碳氟化合物。
- 一種鋰離子二次電池的負極,其特徵在於包含如請求項1所述的鋰離子二次電池的負極材料。
- 如請求項2所述的鋰離子二次電池的負極,其中該鋰離子二次電池的負極係藉由將該鋰離子二次電池的負極材料與導電碳及黏著劑混合並塗佈於鋁箔上所形成。
- 如請求項3所述的鋰離子二次電池的負極,其中該鋰離子二次電池的負極材料之含量為90重量百分比,該導電碳之含量為5重量百分比,該黏著劑之含量為5重量百分比。
- 一種鋰離子二次電池,其特徵在於包含如請求項2至4中任一項所述的鋰離子二次電池的負極。
- 如請求項5所述的鋰離子二次電池,其中該鋰離子二次電池係為鋰離子鈕扣型電池。
- 如請求項5或6所述的鋰離子二次電池,其中該鋰離子二次電池之正極的材料係選自鈷酸鋰、鎳酸鋰、錳酸鋰、三元正極材料、磷酸鋰鐵、磷酸鋰鐵錳、及三元正極材料與磷酸鋰鐵錳結合而成的複合正極材料所構成的群組。
- 一種鋰離子二次電池的負極材料的製備方法,係用於製備如請求項1所述的鋰離子二次電池的負極材料,該製備方法包含下列步驟: 將鈦酸鋰的粉末及聚偏二氟乙烯的粉末混合後,進行燒結,而得到表面包覆有碳氟化合物之改質層的鈦酸鋰,作為該鋰離子二次電池的負極材料。
- 如請求項8所述之鋰離子二次電池的負極材料的製備方法,其中在混合時,該鈦酸鋰的粉末的含量為99重量百分比,該聚偏二氟乙烯的粉末之含量為1重量百分比。
- 如請求項8所述之鋰離子二次電池的負極材料的製備方法,其中燒結為在空氣下以300°C進行2小時。
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