TWI649916B - Positive electrode of lithium ion battery - Google Patents
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- TWI649916B TWI649916B TW106100955A TW106100955A TWI649916B TW I649916 B TWI649916 B TW I649916B TW 106100955 A TW106100955 A TW 106100955A TW 106100955 A TW106100955 A TW 106100955A TW I649916 B TWI649916 B TW I649916B
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- positive electrode
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- active material
- ion battery
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000011149 active material Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000001069 Raman spectroscopy Methods 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 238000005253 cladding Methods 0.000 description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- -1 poly(sodium 4-styrene sulfonate) Polymers 0.000 description 8
- 229910052707 ruthenium Inorganic materials 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 6
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920002550 PolyAPTAC Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920001464 poly(sodium 4-styrenesulfonate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
一種鋰離子電池之正電極，包括一第一集流器、一設置於該第一集流器一側的正電極活性材料層以及一設置於該第一集流器與該正電極活性材料層之間的第一碳材料層，其中該正電極活性材料層包括複數個第一材料顆粒，該第一材料顆粒具有一形成於該第一材料顆粒之一表面的石墨烯殼層。A positive electrode of a lithium ion battery includes a first current collector, a positive electrode active material layer disposed on one side of the first current collector, and a first current collector and the positive electrode active material layer A first layer of carbon material, wherein the layer of positive electrode active material comprises a plurality of first material particles having a graphene shell formed on a surface of one of the first material particles.
Description
本發明有關一種鋰離子電池，尤指一種儲電量提升的鋰離子電池。 The invention relates to a lithium ion battery, in particular to a lithium ion battery with improved storage capacity.
隨著科技的進步以及環保意識的重視，二次電池廣泛地應用於各種領域，例如電動車、移動式電子裝置或航太裝置，以現況來說，二次電池的儲電量未滿足市場所需，因此許多電池廠商極力發展高儲電量的二次電池以解決現有問題。 With the advancement of technology and the importance of environmental awareness, secondary batteries are widely used in various fields, such as electric vehicles, mobile electronic devices or aerospace devices. In the current situation, the storage capacity of secondary batteries does not meet the market demand. Therefore, many battery manufacturers strive to develop secondary batteries with high storage capacity to solve existing problems.
如中華民國發明專利公告第I474543號，提出一種鋰電池，包括一隔離層、一正極結構以及一負極結構，該隔離層具有一第一表面與相對於該第一表面之一第二表面，該正極結構設置於該第一表面，具有一正極層與一正極集電層，該正極層之二側分別連接於該第一表面與該正極集電層，該負極結構設置於該第二表面，具有一負極層與一負極集電層，該負極層之二側分別連接於該第二表面與該負極集電層，其中該正極集電層及/或該負極集電層之材質主要係由一第一碳材與一第二碳材所構成，該第一碳材之比表面積與該第二碳材之比表面積的比值係在2至300之範圍中，於該正極集電層及/或該負極集電層中，該第一碳材與該第二碳材之重量比係在2：1至1：1之範圍中，該第一碳材與該第二碳材係為石墨粉。 For example, the Republic of China Invention Patent Publication No. I474543 proposes a lithium battery including an isolation layer, a positive electrode structure and a negative electrode structure, the separation layer having a first surface and a second surface opposite to the first surface, The positive electrode structure is disposed on the first surface, and has a positive electrode layer and a positive electrode collector layer. The two sides of the positive electrode layer are respectively connected to the first surface and the positive electrode collector layer, and the negative electrode structure is disposed on the second surface. Having a negative electrode layer and a negative electrode collector layer, the two sides of the negative electrode layer are respectively connected to the second surface and the negative electrode collector layer, wherein the material of the positive electrode collector layer and/or the negative electrode collector layer is mainly composed of a first carbon material and a second carbon material, wherein a ratio of a specific surface area of the first carbon material to a specific surface area of the second carbon material is in a range of 2 to 300, and the positive electrode collector layer and/or Or the negative electrode collector layer, the weight ratio of the first carbon material to the second carbon material is in the range of 2:1 to 1:1, and the first carbon material and the second carbon material are graphite powder .
於以上先前技術之中，該正極集電層與該正極層彼此間以及該負極集電層與該負極層彼此間的導電性仍有改善之空間，以提升鋰離子電池的儲電量。 In the above prior art, there is still room for improvement in electrical conductivity between the positive electrode collector layer and the positive electrode layer and between the negative electrode collector layer and the negative electrode layer to improve the storage capacity of the lithium ion battery.
本發明的主要目的，在於解決習知鋰離子電池儲電量不足的問題。 The main object of the present invention is to solve the problem of insufficient storage capacity of a conventional lithium ion battery.
為達上述目的，本發明提供一種鋰離子電池之正電極，包括一第一集流器、一設置於該第一集流器一側的正電極活性材料層以及一設置於該第一集流器與該正電極活性材料層之間的第一碳材料層，其中該正電極活性材料層包括複數個第一材料顆粒，該第一材料顆粒具有一形成於該第一材料顆粒之一表面的石墨烯殼層。 In order to achieve the above object, the present invention provides a positive electrode of a lithium ion battery, comprising a first current collector, a positive electrode active material layer disposed on one side of the first current collector, and a first current collector disposed on the first current collector a first carbon material layer between the device and the positive electrode active material layer, wherein the positive electrode active material layer comprises a plurality of first material particles, the first material particles having a surface formed on one surface of the first material particles Graphene shell layer.
於本發明一實施例中，該第一碳材料層為一石墨烯層，該石墨烯層具有一La介於1μm至50μm之間的直徑以及一介於1至10之間的層數，其中該La係為一由拉曼光譜所獲得石墨群的大小值。 In an embodiment of the invention, the first carbon material layer is a graphene layer having a diameter of La between 1 μm and 50 μm and a number of layers between 1 and 10, wherein the layer La is a size value of a graphite group obtained by Raman spectroscopy.
由以上可知，本發明相較於習知技藝可達到之功效在於： From the above, it can be seen that the achievable effects of the present invention over the prior art are:
(1)於該第一集流器與該正電極活性材料層之間設置大面積石墨烯層，該石墨烯層具有一La介於1μm至50μm之間的直徑(該La係為一由拉曼光譜所獲得石墨群的大小值)，可提升該集流器與該活性材料層之間的導電性。 (1) providing a large-area graphene layer between the first current collector and the positive electrode active material layer, the graphene layer having a diameter of La between 1 μm and 50 μm (the La system is a pull-up The size of the graphite group obtained by the Mann spectrum) enhances the electrical conductivity between the current collector and the active material layer.
(2)由於該正電極活性材料層中的該活性材料顆粒具有該石墨烯殼層，因此可提升該活性材料顆粒的導電性，故該鋰離子電池的總儲電量提高。 (2) Since the active material particles in the positive electrode active material layer have the graphene shell layer, the conductivity of the active material particles can be improved, so that the total storage amount of the lithium ion battery is increased.
10‧‧‧正電極 10‧‧‧ positive electrode
11‧‧‧第一集流器 11‧‧‧First current collector
12‧‧‧正電極活性材料層 12‧‧‧Positive electrode active material layer
121‧‧‧活性材料顆粒 121‧‧‧Active material particles
1210‧‧‧第一材料顆粒 1210‧‧‧First material particles
1211‧‧‧石墨烯殼層 1211‧‧‧graphene shell
13‧‧‧第一碳材料層 13‧‧‧First carbon material layer
20‧‧‧負電極 20‧‧‧Negative electrode
21‧‧‧第二集流器 21‧‧‧Second current collector
22‧‧‧負電極活性材料層 22‧‧‧Negative electrode active material layer
23‧‧‧第二碳材料層 23‧‧‧Second carbon material layer
231‧‧‧石墨烯層 231‧‧‧graphene layer
232‧‧‧矽顆粒 232‧‧‧矽 particles
233‧‧‧第一包覆層 233‧‧‧First cladding
234‧‧‧第二包覆層 234‧‧‧Second coating
235‧‧‧第三包覆層 235‧‧‧ third cladding
30‧‧‧隔離膜 30‧‧‧Separator
『圖1』，為本發明一實施例的鋰離子電池結構示意圖。 FIG. 1 is a schematic structural view of a lithium ion battery according to an embodiment of the present invention.
『圖2』，為本發明又一實施例的第二碳材料層部分結構示意圖。 FIG. 2 is a partial structural view of a second carbon material layer according to still another embodiment of the present invention.
有關本發明的詳細說明及技術內容，現就配合圖式說明如下： The detailed description and technical content of the present invention will now be described as follows:
請搭配參閱『圖1』、『圖2』所示，為本發明一實施例的鋰離子電池結構示意圖，包括一正電極10、一負電極20以及一隔離膜30，該正電極10包括一第一集流器11、一正電極活性材料層12以及一第一碳材料層13，該第一集流器11的材質可為鋁、銅、鐵、鎳、鉑、鎢、鉬、鉭、鈮、釩、鉻、鈦、鋯或上述組合。該正電極活性材料層12設置於該第一集流器11一側，於一實施例，該正電極活性材料層12包括複數個活性材料顆粒121，該活性材料顆粒121包括一第一材料顆粒1210以及一形成於該第一材料顆粒1210之一表面的石墨烯殼層1211，該活性材料顆粒121係彼此堆疊並接觸，其中該第一材料顆粒1210可為磷酸鋰鐵、鋰鎳鈷、鋰鎳鈷錳、鈷酸鋰、鎳酸鋰、錳酸鋰或上述組合；在該第一材料顆粒1210上形成該石墨烯殼層1211的方法並無特別限制，舉例來說，可利用一混拌造粒法將一石墨烯塗佈於該第一材料顆粒1210的該表面，接著透過一具有一介於50℃至300℃之間的烘烤溫度進行烘烤而製成，此時，該第一材料顆粒1210之該表面係部分地、或完全地經該石墨烯包覆。 Referring to FIG. 1 and FIG. 2, a schematic diagram of a lithium ion battery according to an embodiment of the present invention includes a positive electrode 10, a negative electrode 20 and a separator 30. The positive electrode 10 includes a first electrode. a first current collector 11, a positive electrode active material layer 12, and a first carbon material layer 13, the first current collector 11 may be made of aluminum, copper, iron, nickel, platinum, tungsten, molybdenum, niobium, Niobium, vanadium, chromium, titanium, zirconium or combinations thereof. The positive electrode active material layer 12 is disposed on the side of the first current collector 11. In an embodiment, the positive electrode active material layer 12 includes a plurality of active material particles 121, and the active material particles 121 include a first material particle. 1210 and a graphene shell layer 1211 formed on one surface of the first material particle 1210, the active material particles 121 are stacked and in contact with each other, wherein the first material particle 1210 may be lithium iron phosphate, lithium nickel cobalt, lithium Nickel-cobalt-manganese, lithium cobaltate, lithium nickelate, lithium manganate or a combination thereof; the method of forming the graphene shell layer 1211 on the first material particles 1210 is not particularly limited, and for example, a mixture may be utilized. The granulation method applies a graphene to the surface of the first material particle 1210, and then is formed by baking at a baking temperature of between 50 ° C and 300 ° C. At this time, the first The surface of the material particles 1210 is partially or completely coated with the graphene.
該第一碳材料層13設置於該第一集流器11與該正電極活性材料層12之間，於本發明中，該第一碳材料層13為一石墨烯層，該石墨烯層具有一La介於1μm至50μm之間的直徑以及一介於1至10之間的層數，其中該La係為一由拉曼光譜所獲得石墨群的大小值。 The first carbon material layer 13 is disposed between the first current collector 11 and the positive electrode active material layer 12. In the present invention, the first carbon material layer 13 is a graphene layer, and the graphene layer has A La is between 1 μm and 50 μm in diameter and a number between 1 and 10, wherein the La is a size of the graphite group obtained by Raman spectroscopy.
該負電極20與該正電極10分離設置，且該負電極20包括一第二集流器21、一負電極活性材料層22以及一第二碳材料層23，該第二集流器21的材質可為鋁、銅、鐵、鎳、鉑、鎢、鉬、鉭、鈮、釩、鉻、鈦、鋯或上述組合。該負電極活性材料層22設置於該第二集流器21一側，於一實施例，該負電極活性材料層22可為習知適用的碳材料，於一較佳實施例中，該負電極活性材料層22包括一La介於1μm至50μm之間的直徑的碳材料(其中該 La係為一由拉曼光譜所獲得石墨群的大小值)，譬如一石墨、一石墨烯、或其組合。該第二碳材料層23設置於該第二集流器21與該負電極活性材料層22之間，於本發明中，該第二碳材料層23為一包括1至10層大面積的石墨烯層231，該石墨烯層231具有一La介於1μm至50μm之間的直徑。 The negative electrode 20 is disposed separately from the positive electrode 10, and the negative electrode 20 includes a second current collector 21, a negative electrode active material layer 22, and a second carbon material layer 23, the second current collector 21 The material may be aluminum, copper, iron, nickel, platinum, tungsten, molybdenum, niobium, tantalum, vanadium, chromium, titanium, zirconium or a combination thereof. The negative electrode active material layer 22 is disposed on the side of the second current collector 21. In one embodiment, the negative electrode active material layer 22 may be a conventionally applicable carbon material. In a preferred embodiment, the negative The electrode active material layer 22 includes a carbon material having a diameter of La between 1 μm and 50 μm (wherein La is a size of a graphite group obtained by Raman spectroscopy, such as graphite, graphene, or a combination thereof. The second carbon material layer 23 is disposed between the second current collector 21 and the negative electrode active material layer 22. In the present invention, the second carbon material layer 23 is a graphite having a large area of 1 to 10 layers. The olefin layer 231 has a diameter of La between 1 μm and 50 μm.
請續參考『圖2』。於一實施例，該第二碳材料層23包括複數個矽顆粒232，該些矽顆粒232均與該石墨烯層231接觸，其中該矽顆粒232具有一介於10nm至100nm之間的粒徑，例如一以矽烯組成的球體。由於該鋰離子電池充放電的過程中，鋰離子會自由地進出該矽顆粒232，導致該矽顆粒232的體積劇烈改變，若選用較大粒徑的該矽顆粒232會導致該矽顆粒232崩解而失去提升儲電量的效果，故本案選用相對於鋰離子較小粒徑的該矽顆粒232，可防止該矽顆粒因劇烈的體積變化而崩解，以提升該鋰離子電池的使用壽命。 Please continue to refer to Figure 2. In one embodiment, the second carbon material layer 23 includes a plurality of germanium particles 232, each of which is in contact with the graphene layer 231, wherein the germanium particles 232 have a particle size of between 10 nm and 100 nm. For example, a sphere composed of terpene. During the charging and discharging process of the lithium ion battery, lithium ions can freely enter and exit the ruthenium particles 232, resulting in a drastic change in the volume of the ruthenium particles 232. If the larger particle size of the ruthenium particles 232 is selected, the ruthenium particles 232 will collapse. The solution loses the effect of increasing the storage capacity. Therefore, the ruthenium particles 232 having a smaller particle size relative to the lithium ion are used in the present case to prevent the ruthenium particles from disintegrating due to a drastic volume change, thereby improving the service life of the lithium ion battery.
為了強化該矽顆粒232與該石墨烯層231的結合，於一實施例中，該矽顆粒232之表面以一第一包覆層233包覆，且同時該石墨烯層231以一第二包覆層234包覆。關於該第一包覆層233與該第二包覆層234的材料並無特別限制，只要該第一包覆層233與該第二包覆層234彼此之間可產生一化學鍵結而連結即可，譬如，該第一包覆層233與該第二包覆層234交聯、或者該第一包覆層233與該第二包覆層234分別攜帶相反電性而連結，然本發明並不僅限於此。 In order to strengthen the bonding of the ruthenium particles 232 and the graphene layer 231, in one embodiment, the surface of the ruthenium particles 232 is coated with a first cladding layer 233, and at the same time, the graphene layer 231 is a second package. The cover 234 is coated. The material of the first cladding layer 233 and the second cladding layer 234 is not particularly limited as long as the first cladding layer 233 and the second cladding layer 234 are chemically bonded to each other and connected. For example, the first cladding layer 233 and the second cladding layer 234 are cross-linked, or the first cladding layer 233 and the second cladding layer 234 respectively carry opposite electrical properties and are connected. Not limited to this.
關於該第一包覆層233的材料的非限制性實例包括：具有磺酸官能基的高分子，如聚苯乙烯磺酸鈉鹽(poly(sodium 4-styrene sulfonate)、聚(2-丙烯醯胺-2-甲基丙磺酸(poly(2-acrylamido-2-methyl-1-propanesulfonic acid)；具有碳酸官能基的高分子；陽離子交換樹脂；聚乙烯醇(polyvinyl alcohol)：及/或聚丙烯酸(polyacrylic acid)或聚丙烯酸鈉鹽(poly(sodium acrylate))。至於該第二包覆層234的材料的非限制性實例包括：聚四級銨鹽；陰離子交換樹脂；聚乙烯醇(polyvinyl alcohol)；聚二丙烯基二甲基氯化銨(polydiallyldimethylammonium chloride)、十二烷基三甲基溴化銨(dodecyltrimethylammonium bromide)、聚丙烯醯胺丙基三甲基氯化銨(poly(acrylamido-N-propyl trimethyl ammonium chloride)、聚3-甲基丙醯胺丙基三甲基氯化銨(poly((3-methacryloylamino-propyl trimethylammonium chloride)、聚氫氧化氯烯丙胺(poly(allylamine hydrochloride)、聚二甲基氨基甲基氯季銨鹽(poly(dimethylaminoethylacrylate methylchloride quat)、及/或聚甲基丙烯酸二甲氨基甲基氯季銨鹽(poly(dimethylaminoethylmethacrylate methylchloride quat)。 Non-limiting examples of the material of the first cladding layer 233 include: a polymer having a sulfonic acid functional group such as poly(sodium 4-styrene sulfonate), poly(2-propene oxime). Poly-2-ylpropamido-2-methyl-1-propanesulfonic acid; a polymer having a carbonic acid functional group; a cation exchange resin; a polyvinyl alcohol: and/or a poly Polyacrylic acid or polyacrylic acid sodium salt (poly(sodium) Acrylate)). Non-limiting examples of the material of the second cladding layer 234 include: a polyquaternary ammonium salt; an anion exchange resin; polyvinyl alcohol; polydiallyldimethylammonium chloride, Dodecyltrimethylammonium bromide, poly(acrylamido-N-propyl trimethyl ammonium chloride), poly-3-methylpropionamine propyl Poly(dimethylaminoethylacrylate methyl chloride quat), poly(dimethylaminoethylacrylate methyl chloride quat), poly(dimethylaminoethyl acrylate quaternary ammonium poly(dimethylaminoethyl acrylate) And/or poly(dimethylaminoethylmethacrylate methylchloride quat).
為了更確保該石墨烯層231與該矽顆粒232之間的結合力，提升導電效果，進而改善該二次電池的充放電效率，在該第一包覆層233與該第二包覆層234之表面更包括一第三包覆層235，以確保該矽顆粒232有效地與該石墨烯層231之表面接觸。該第三包覆層235的材料舉例可為含碳導電膜，但本發明對此並無特別限制。 In order to further ensure the bonding force between the graphene layer 231 and the tantalum particles 232, the conductive effect is enhanced, and the charge and discharge efficiency of the secondary battery is improved, in the first cladding layer 233 and the second cladding layer 234. The surface further includes a third cladding layer 235 to ensure that the tantalum particles 232 are effectively in contact with the surface of the graphene layer 231. The material of the third cladding layer 235 may be, for example, a carbon-containing conductive film, but the present invention is not particularly limited thereto.
該隔離膜30夾設於該正電極10與該負電極20之間，該隔離膜30的材質舉例可為聚乙烯(Polyethylene，簡稱PE)、聚丙烯(Polypropylene，簡稱PP)、或其組合，本發明不以此為限。 The separator 30 is interposed between the positive electrode 10 and the negative electrode 20. The material of the separator 30 may be polyethylene (Polyethylene, PE, PP, or a combination thereof). The invention is not limited thereto.
綜上所述，由於本案係分別於該第一集流器與該正電極活性材料層之間以及於該第二集流器與該負電極活性材料層之間設置大面積的該石墨烯層，以提升該集流器與該活性材料層之間的導電性；另外，由於該正電極活性材料層的該第一材料顆粒的該表面具有該石墨烯殼層，因此可提升該第一材料顆粒的導電性，故該鋰離子電池的總儲電量提高。 In summary, the present invention provides a large area of the graphene layer between the first current collector and the positive electrode active material layer and between the second current collector and the negative electrode active material layer. To enhance the electrical conductivity between the current collector and the active material layer; in addition, since the surface of the first material particle of the positive electrode active material layer has the graphene shell layer, the first material can be lifted The conductivity of the particles increases the total storage capacity of the lithium ion battery.
以上已將本發明做一詳細說明，惟以上所述者，僅為本發明的一較佳實施例而已，當不能限定本發明實施的範圍。即凡依本發明申請範圍所作的均等變化與修飾等，皆應仍屬本發明的專利涵蓋範圍內。 The present invention has been described in detail above, but the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the scope of the invention. That is, the equivalent changes and modifications made by the scope of the present application should remain within the scope of the patent of the present invention.
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| TWI469411B (en) * | 2012-07-13 | 2015-01-11 | Hon Hai Prec Ind Co Ltd | Method for making thin film lithium ion battery |
| TWI474543B (en) * | 2013-01-14 | 2015-02-21 | Univ Yuan Ze | Lithium battery and manufacturing method for electrode and current collector thereof |
| CN103840131A (en) * | 2014-03-27 | 2014-06-04 | 合肥国轩高科动力能源股份公司 | Novel lithium ion battery |
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