TWI770796B - Conductive structure and battery - Google Patents

Conductive structure and battery Download PDF

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TWI770796B
TWI770796B TW110103522A TW110103522A TWI770796B TW I770796 B TWI770796 B TW I770796B TW 110103522 A TW110103522 A TW 110103522A TW 110103522 A TW110103522 A TW 110103522A TW I770796 B TWI770796 B TW I770796B
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conductive layer
conductive
layer
graphene
conductive structure
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TW202230874A (en
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魏松煙
鄭嘉晉
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優材科技有限公司
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a conductive structure and a battery including the conductive structure. The conductive structure includes a metal substrate, a first conductive layer, a graphene layer and a second conductive layer. The first conductive layer is disposed at the metal substrate. The first conductive layer includes a plurality of carbon nanotubes. The graphene layer is disposed between the metal substrate and the first conductive layer. The second conductive layer is disposed at the first conductive layer, and the material of the second conductive layer is located in the gaps between the carbon nanotubes. In addition to excellent electrical conductivity, the present invention can also increase the energy density of the battery.

Description

導電結構與電池Conductive Structures and Batteries

本發明關於一種導電結構，特別關於一種應用於電池正極的導電結構與電池。 The present invention relates to a conductive structure, in particular to a conductive structure and a battery applied to a positive electrode of a battery.

鋰離子電池是目前電動車，乃至於時下絕大多數電子產品中最常用的電池種類，它從1970年誕生至今將近半個世紀了，其優勢是能量密度高、循環使用壽命長。市面上出現的六類鋰電池分別是鈦酸鋰、鈷酸鋰、錳酸鋰、磷酸鐵鋰、鎳鈷錳和鎳鈷鋁鋰電池(鎳鈷錳和鎳鈷鋁鋰電池可稱為三元鋰電池)。從能量密度和安全性綜合來看，綜合性能較好的磷酸鐵鋰電池和三元鋰電池已成為了目前電動車動力電池的主流。 Lithium-ion battery is currently the most commonly used type of battery in electric vehicles and even most electronic products. It has been around for nearly half a century since its birth in 1970. Its advantages are high energy density and long cycle life. The six types of lithium batteries that appear on the market are lithium titanate, lithium cobaltate, lithium manganate, lithium iron phosphate, nickel-cobalt-manganese and nickel-cobalt-aluminum lithium batteries (nickel-cobalt-manganese and nickel-cobalt-aluminum lithium batteries can be called ternary batteries. lithium battery). From the comprehensive point of view of energy density and safety, lithium iron phosphate batteries and ternary lithium batteries with better comprehensive performance have become the mainstream of electric vehicle power batteries.

目前鋰電池主要是按照正極材料的不同來分類，因為負極材料(主要以碳材料為主)對電池能量密度的影響不大，所以現在主要是通過不斷改進正極材料來提升電池的性能。在習知技術中，正極材料一般是以錳酸鋰(LiMn2O4)、磷酸鐵鋰(LiFePO4)、或鎳鈷鋰(LiNiCOO2)等為主要材料，並在正極活性物質中再加入導電劑(例如碳黑)，並塗覆在金屬基體(例如鋁)上。 At present, lithium batteries are mainly classified according to the difference of positive electrode materials. Because the negative electrode materials (mainly carbon materials) have little effect on the energy density of the battery, the performance of the battery is mainly improved by continuously improving the positive electrode material. In the prior art, the positive electrode material is generally made of lithium manganate (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ), or lithium nickel cobalt (LiNiCOO 2 ) as the main material, and is added to the positive electrode active material. Conductive agent (eg carbon black) and coated on a metal substrate (eg aluminium).

本發明的目的為提供一種應用於電池正極的導電結構與包括該導電結構的電池。本發明的導電結構除了具有極佳的導電性外，還可提高電池的能量密度。 The purpose of the present invention is to provide a conductive structure applied to a positive electrode of a battery and a battery including the conductive structure. Besides excellent conductivity, the conductive structure of the present invention can also improve the energy density of the battery.

本發明提出一種導電結構，包括一金屬基體、一第一導電層、一石墨烯層以及一第二導電層。第一導電層設置於金屬基體，第一導電層包括多個奈 米碳管；石墨烯層設置於金屬基體與第一導電層之間；第二導電層設置於第一導電層，且第二導電層的材料位於該些奈米碳管之間的間隙。 The present invention provides a conductive structure, which includes a metal substrate, a first conductive layer, a graphene layer and a second conductive layer. The first conductive layer is disposed on the metal base, and the first conductive layer includes a plurality of nanometers carbon nanotubes; the graphene layer is arranged between the metal substrate and the first conductive layer; the second conductive layer is arranged on the first conductive layer, and the material of the second conductive layer is located in the gap between the carbon nanotubes.

在一實施例中，金屬基體的材料包括鋁。 In one embodiment, the material of the metal matrix includes aluminum.

在一實施例中，第二導電層的材料更覆蓋第一導電層遠離石墨烯層的表面。 In one embodiment, the material of the second conductive layer further covers the surface of the first conductive layer away from the graphene layer.

在一實施例中，石墨烯層至少覆蓋金屬基體的部份表面。 In one embodiment, the graphene layer covers at least part of the surface of the metal substrate.

在一實施例中，該些奈米碳管的軸向方向垂直於石墨烯層的表面。 In one embodiment, the axial direction of the carbon nanotubes is perpendicular to the surface of the graphene layer.

在一實施例中，該些奈米碳管的軸向方向垂直於石墨烯層及金屬基體的表面。 In one embodiment, the axial direction of the carbon nanotubes is perpendicular to the surface of the graphene layer and the metal substrate.

在一實施例中，第二導電層的材料包括石墨烯、人造石墨、天然石墨、碳黑(Carbon black)、導電金屬粒子、或其組合。 In one embodiment, the material of the second conductive layer includes graphene, artificial graphite, natural graphite, carbon black, conductive metal particles, or a combination thereof.

在一實施例中，導電金屬粒子的材料包括銀、銅、金、鋁、或鉑，或其組合。 In one embodiment, the material of the conductive metal particles includes silver, copper, gold, aluminum, or platinum, or a combination thereof.

在一實施例中，導電結構可應用於鋰電池的正極。 In one embodiment, the conductive structure can be applied to the positive electrode of a lithium battery.

本發明還提出一種電池，包括一正極及一負極，負極與正極對應設置；其中，正極包括上述實施例的導電結構。 The present invention also provides a battery, comprising a positive electrode and a negative electrode, wherein the negative electrode and the positive electrode are arranged correspondingly; wherein, the positive electrode includes the conductive structure of the above embodiment.

承上所述，在本發明的導電結構與包括該導電結構的電池中，第一導電層設置於金屬基體，並包括多個奈米碳管；石墨烯層設置於金屬基體與第一導電層之間；第二導電層設置於第一導電層，且第二導電層的材料位於第一導電層的該些奈米碳管之間的間隙。藉此，本發明並不以碳黑做為導電劑，而是以第一導電層(包括奈米碳管)、石墨烯層及第二導電層(例如包括石墨烯)作為金屬基體的導電劑，由於第一導電層、石墨烯層及第二導電層皆具有極佳的導電性，因此可使導電結構也具有相當好的導電性而可應用於電池的正極，藉此提升電池的能量密度。 Continuing from the above, in the conductive structure and the battery including the conductive structure of the present invention, the first conductive layer is disposed on the metal substrate and includes a plurality of carbon nanotubes; the graphene layer is disposed on the metal substrate and the first conductive layer The second conductive layer is disposed on the first conductive layer, and the material of the second conductive layer is located in the gap between the carbon nanotubes of the first conductive layer. Therefore, the present invention does not use carbon black as the conductive agent, but uses the first conductive layer (including carbon nanotubes), the graphene layer and the second conductive layer (for example, including graphene) as the conductive agent for the metal matrix , since the first conductive layer, the graphene layer and the second conductive layer all have excellent conductivity, the conductive structure can also have good conductivity and can be applied to the positive electrode of the battery, thereby increasing the energy density of the battery .

1,1a:導電結構 1,1a: Conductive structure

11:金屬基體 11: Metal matrix

111:表面 111: Surface

12:第一導電層 12: The first conductive layer

121:奈米碳管 121: Carbon Nanotubes

13:石墨烯層 13: Graphene layer

14:第二導電層 14: The second conductive layer

圖1為本發明一實施例的導電結構的示意圖。 FIG. 1 is a schematic diagram of a conductive structure according to an embodiment of the present invention.

圖2為本發明另一實施例的導電結構的示意圖。 FIG. 2 is a schematic diagram of a conductive structure according to another embodiment of the present invention.

以下將參照相關圖式，說明依本發明一些實施例之應用於電池正極的導電結構與包括該導電結構的電池，其中相同的元件將以相同的參照符號加以說明。 A conductive structure applied to a positive electrode of a battery and a battery including the conductive structure according to some embodiments of the present invention will be described below with reference to the related drawings, wherein the same elements will be described with the same reference symbols.

本發明的導電結構可應用於鋰電池的正極，除了具有極佳的導電性外，還可提高鋰電池的能量密度。 The conductive structure of the present invention can be applied to the positive electrode of a lithium battery, and besides having excellent conductivity, the energy density of the lithium battery can also be improved.

圖1為本發明一實施例的導電結構的示意圖。如圖1所示，本實施例的導電結構1包括一金屬基體11、一第一導電層12、一石墨烯層13以及一第二導電層14。 FIG. 1 is a schematic diagram of a conductive structure according to an embodiment of the present invention. As shown in FIG. 1 , the conductive structure 1 of this embodiment includes a metal base 11 , a first conductive layer 12 , a graphene layer 13 and a second conductive layer 14 .

金屬基體11例如但不限於高電導率的金屬片或金屬箔，其材料可例如但不限於包括鋁。 The metal substrate 11 is, for example, but not limited to, a high-conductivity metal sheet or metal foil, and its material may include, for example, but not limited to, aluminum.

第一導電層12設置於金屬基體11，並包括多個奈米碳管121。而石墨烯層13設置於金屬基體11與第一導電層12之間。於此，石墨烯層13係設置於金屬基體11的表面111，使第一導電層12可透過石墨烯層13間接設置於金屬基體11上。本實施例的石墨烯層13包括多個石墨烯微片，其位於金屬基體11與第一導電層12之間，且石墨烯層13至少可覆蓋金屬基體11的部份表面111。具體來說，石墨烯層13可全面性地覆蓋在金屬基體11的表面111，或是團聚成島狀且彼此分離地覆蓋在金屬基體11的部分表面111。本實施例的石墨烯層13是以全面性地覆蓋在金屬基體11的表面111為例。因此，第一導電層12之該些奈米碳管121的軸向方向是垂直於石墨烯層13的表面。 The first conductive layer 12 is disposed on the metal base 11 and includes a plurality of carbon nanotubes 121 . The graphene layer 13 is disposed between the metal base 11 and the first conductive layer 12 . Here, the graphene layer 13 is disposed on the surface 111 of the metal base 11 , so that the first conductive layer 12 can be indirectly disposed on the metal base 11 through the graphene layer 13 . The graphene layer 13 in this embodiment includes a plurality of graphene microplates located between the metal substrate 11 and the first conductive layer 12 , and the graphene layer 13 can cover at least part of the surface 111 of the metal substrate 11 . Specifically, the graphene layer 13 can completely cover the surface 111 of the metal base 11 , or agglomerate into an island shape and cover part of the surface 111 of the metal base 11 separately from each other. The graphene layer 13 in this embodiment is taken as an example to cover the surface 111 of the metal base 11 comprehensively. Therefore, the axial direction of the carbon nanotubes 121 of the first conductive layer 12 is perpendicular to the surface of the graphene layer 13 .

在一些實施例中，如果石墨烯層13是團聚成島狀且彼此分離地覆蓋在金屬基體11的部分表面111的話，則有部分的奈米碳管121的軸向方向垂直於石墨烯層13，但另一部分的奈米碳管121的軸向方向則垂直於材料例如是鋁的金屬基體11的表面111。另外，如果石墨烯層13覆蓋在金屬基體11的部分表面111，且金屬基體11的材料是銅的話，則奈米碳管121只會成長在石墨烯層13(即軸向 方向垂直於石墨烯層13)，並不會成長在銅材料的金屬基體11，視金屬基體11的材料及石墨烯層13的覆蓋率來決定奈米碳管121之軸向方向的垂直方式。 In some embodiments, if the graphene layers 13 are agglomerated into islands and cover part of the surface 111 of the metal substrate 11 separately from each other, the axial direction of some carbon nanotubes 121 is perpendicular to the graphene layer 13, However, the axial direction of the other part of the carbon nanotubes 121 is perpendicular to the surface 111 of the metal substrate 11 which is made of aluminum, for example. In addition, if the graphene layer 13 covers part of the surface 111 of the metal base 11, and the material of the metal base 11 is copper, the carbon nanotubes 121 will only grow on the graphene layer 13 (ie, the axial direction). The direction is perpendicular to the graphene layer 13), and will not grow on the metal substrate 11 of copper material.

在一些實施例中，前述的石墨烯微片的厚度可大於等於0.3奈米(nm)，且小於等於3奈米(0.3nm

Figure 110103522-A0305-02-0006-1
厚度
Figure 110103522-A0305-02-0006-2
3nm)，而各石墨烯微片的片徑(即最大寬度)可大於等於1微米，且小於等於30微米(1μm
Figure 110103522-A0305-02-0006-3
片徑
Figure 110103522-A0305-02-0006-4
30μm)。 In some embodiments, the thickness of the aforementioned graphene microplates may be greater than or equal to 0.3 nanometers (nm) and less than or equal to 3 nanometers (0.3 nm).
Figure 110103522-A0305-02-0006-1
thickness
Figure 110103522-A0305-02-0006-2
3nm), and the sheet diameter (that is, the maximum width) of each graphene microplate can be greater than or equal to 1 micron and less than or equal to 30 microns (1 μm
Figure 110103522-A0305-02-0006-3
Diameter
Figure 110103522-A0305-02-0006-4
30 μm).

第二導電層14設置於第一導電層12，且第二導電層14的材料位於第一導電層12之該些奈米碳管121之間的間隙。第二導電層14的材料可例如但不限於包括石墨烯、人造石墨、天然石墨、碳黑、導電金屬粒子、或其組合。而導電金屬粒子的材料包括銀、銅、金、鋁、或鉑，或其組合，並不限制。本實施例之第二導電層14的材料例如是以石墨烯為例。具體來說，可將石墨烯微片與溶劑(例如但不限於水)均勻混合後形成漿料，並將具有流動性的漿料以例如塗佈、印刷、或其他適當的方式設置在第一導電層12上，使第二導電層14的材料填入奈米碳管121之間的間隙(較佳者為填滿所有間隙)，待乾燥(去除溶劑)、固化後形成第二導電層14，藉此提高導電性。當然，因製程或其他因素，奈米碳管121之間的間隙可能無法被第二導電層14的材料(石墨烯)完全填滿。 The second conductive layer 14 is disposed on the first conductive layer 12 , and the material of the second conductive layer 14 is located in the gaps between the carbon nanotubes 121 of the first conductive layer 12 . The material of the second conductive layer 14 may include, for example, but not limited to, graphene, artificial graphite, natural graphite, carbon black, conductive metal particles, or a combination thereof. The material of the conductive metal particles includes silver, copper, gold, aluminum, or platinum, or a combination thereof, which is not limited. The material of the second conductive layer 14 in this embodiment is, for example, graphene. Specifically, the graphene micro-sheets can be uniformly mixed with a solvent (such as but not limited to water) to form a slurry, and the fluid slurry can be placed on the first On the conductive layer 12, the material of the second conductive layer 14 is filled into the gaps between the carbon nanotubes 121 (preferably, all gaps are filled), and the second conductive layer 14 is formed after drying (removing the solvent) and curing. , thereby increasing the conductivity. Of course, due to the manufacturing process or other factors, the gaps between the carbon nanotubes 121 may not be completely filled by the material (graphene) of the second conductive layer 14 .

承上，在習知技術中，是以碳黑作為金屬基體11的導電劑，但在本實施例的導電結構1中，第一導電層12設置於金屬基體11，並包括多個奈米碳管121，石墨烯層13設置於金屬基體11與第一導電層12之間，第二導電層14設置於第一導電層12，且第二導電層14的材料位於第一導電層12之該些奈米碳管121之間的間隙。藉此，本實施例並不以碳黑作為導電劑，而是以第一導電層12(包括奈米碳管121)、石墨烯層13及第二導電層14(例如包括石墨烯)作為金屬基體11的導電劑，由於第一導電層12、石墨烯層13及第二導電層14皆具有極佳的導電性，因此可使導電結構1也具有相當好的導電性而可應用於鋰電池的正極，藉此提升鋰電池的能量密度。 As mentioned above, in the prior art, carbon black is used as the conductive agent of the metal matrix 11 , but in the conductive structure 1 of this embodiment, the first conductive layer 12 is disposed on the metal matrix 11 and includes a plurality of nanocarbons The tube 121 , the graphene layer 13 is arranged between the metal base 11 and the first conductive layer 12 , the second conductive layer 14 is arranged on the first conductive layer 12 , and the material of the second conductive layer 14 is located on the side of the first conductive layer 12 . gaps between the carbon nanotubes 121 . Therefore, in this embodiment, carbon black is not used as the conductive agent, but the first conductive layer 12 (including carbon nanotubes 121 ), the graphene layer 13 and the second conductive layer 14 (for example, including graphene) are used as metals The conductive agent of the substrate 11, because the first conductive layer 12, the graphene layer 13 and the second conductive layer 14 all have excellent conductivity, so the conductive structure 1 can also have very good conductivity and can be applied to lithium batteries The positive electrode of the lithium battery improves the energy density of the lithium battery.

請參照圖2所示，其為本發明另一實施例的導電結構的示意圖。如圖2所示，本實施例的導電結構1a與前述實施例的導電結構1其元件組成及各元件的連接關係大致相同。不同之處在於，本實施例的導電結構1a的第二導電層14的 材料除了填滿奈米碳管121之間的間隙外，還覆蓋第一導電層12遠離石墨烯層13的表面(即覆蓋第一導電層12的表面)。 Please refer to FIG. 2 , which is a schematic diagram of a conductive structure according to another embodiment of the present invention. As shown in FIG. 2 , the conductive structure 1 a of the present embodiment is substantially the same as the conductive structure 1 of the previous embodiment in terms of the component composition and the connection relationship between the components. The difference is that the second conductive layer 14 of the conductive structure 1a of this embodiment has In addition to filling the gaps between the carbon nanotubes 121 , the material also covers the surface of the first conductive layer 12 away from the graphene layer 13 (ie, covers the surface of the first conductive layer 12 ).

此外，本發明還提出一種電池，其可包括兩個電極：正極及與該正極對應設置的負極。其中，正極可包括上述的導電結構1或1a，或其變化態樣，具體技術內容請參照上述，在此不再多作說明。前述的電池例如但不限於鈦酸鋰、鈷酸鋰、錳酸鋰、磷酸鐵鋰、鎳鈷錳、或鎳鈷鋁等鋰電池。 In addition, the present invention also provides a battery, which may include two electrodes: a positive electrode and a negative electrode corresponding to the positive electrode. Wherein, the positive electrode may include the above-mentioned conductive structure 1 or 1a, or a modified form thereof. For the specific technical content, please refer to the above, which will not be further described here. The aforementioned batteries are, for example, but not limited to, lithium titanate, lithium cobaltate, lithium manganate, lithium iron phosphate, nickel cobalt manganese, or nickel cobalt aluminum and other lithium batteries.

綜上所述，在本發明的導電結構與包括該導電結構的電池中，第一導電層設置於金屬基體，並包括多個奈米碳管；石墨烯層設置於金屬基體與第一導電層之間；第二導電層設置於第一導電層，且第二導電層的材料位於第一導電層的該些奈米碳管之間的間隙。藉此，本發明並不以碳黑作為導電劑，而是以第一導電層(包括奈米碳管)、石墨烯層及第二導電層(例如包括石墨烯)作為金屬基體的導電劑，由於第一導電層、石墨烯層及第二導電層皆具有極佳的導電性，因此可使導電結構也具有相當好的導電性而可應用於電池的正極，藉此提升電池的能量密度。 To sum up, in the conductive structure of the present invention and the battery including the conductive structure, the first conductive layer is disposed on the metal substrate and includes a plurality of carbon nanotubes; the graphene layer is disposed on the metal substrate and the first conductive layer The second conductive layer is disposed on the first conductive layer, and the material of the second conductive layer is located in the gap between the carbon nanotubes of the first conductive layer. Therefore, the present invention does not use carbon black as the conductive agent, but uses the first conductive layer (including carbon nanotubes), the graphene layer and the second conductive layer (for example, including graphene) as the conductive agent of the metal matrix, Since the first conductive layer, the graphene layer and the second conductive layer all have excellent conductivity, the conductive structure can also have very good conductivity and can be applied to the positive electrode of the battery, thereby increasing the energy density of the battery.

以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。 The above description is exemplary only, not limiting. Any equivalent modifications or changes that do not depart from the spirit and scope of the present invention shall be included in the appended patent application scope.

1:導電結構 1: Conductive structure

11:金屬基體 11: Metal matrix

111:表面 111: Surface

12:第一導電層 12: The first conductive layer

121:奈米碳管 121: Carbon Nanotubes

13:石墨烯層 13: Graphene layer

14:第二導電層 14: The second conductive layer

Claims (9)

一種導電結構，包括：一金屬基體；一第一導電層，設置於該金屬基體，該第一導電層包括多個奈米碳管；一石墨烯層，設置於該金屬基體與該第一導電層之間；以及一第二導電層，設置於該第一導電層，且該第二導電層的材料位於該些奈米碳管之間的間隙；其中，該第二導電層的材料更覆蓋該第一導電層遠離該石墨烯層的表面。 A conductive structure, comprising: a metal substrate; a first conductive layer disposed on the metal substrate, the first conductive layer comprising a plurality of carbon nanotubes; a graphene layer disposed on the metal substrate and the first conductive layer between layers; and a second conductive layer disposed on the first conductive layer, and the material of the second conductive layer is located in the gap between the carbon nanotubes; wherein, the material of the second conductive layer further covers The first conductive layer is away from the surface of the graphene layer. 如請求項1所述的導電結構，其中該金屬基體的材料包括鋁。 The conductive structure of claim 1, wherein the material of the metal matrix comprises aluminum. 如請求項1所述的導電結構，其中該石墨烯層至少覆蓋該金屬基體的部份表面。 The conductive structure of claim 1, wherein the graphene layer covers at least a part of the surface of the metal substrate. 如請求項1所述的導電結構，其中該些奈米碳管的軸向方向垂直於該石墨烯層的表面。 The conductive structure of claim 1, wherein the axial direction of the carbon nanotubes is perpendicular to the surface of the graphene layer. 如請求項1所述的導電結構，其中該些奈米碳管的軸向方向垂直於該石墨烯層及該金屬基體的表面。 The conductive structure of claim 1, wherein the axial direction of the carbon nanotubes is perpendicular to the surface of the graphene layer and the metal substrate. 如請求項1所述的導電結構，其中該第二導電層的材料包括石墨烯、人造石墨、天然石墨、碳黑、導電金屬粒子、或其組合。 The conductive structure of claim 1, wherein the material of the second conductive layer comprises graphene, artificial graphite, natural graphite, carbon black, conductive metal particles, or a combination thereof. 如請求項6所述的導電結構，其中該導電金屬粒子的材料包括銀、銅、金、鋁、或鉑，或其組合。 The conductive structure of claim 6, wherein the material of the conductive metal particles comprises silver, copper, gold, aluminum, or platinum, or a combination thereof. 如請求項1所述的導電結構，其應用於鋰電池的正極。 The conductive structure according to claim 1, which is applied to a positive electrode of a lithium battery. 一種電池，包括一正極及一負極，該負極與該正極對應設置；其中，該正極包括如請求項1至7中任一項所述的導電結構。 A battery includes a positive electrode and a negative electrode, the negative electrode is arranged corresponding to the positive electrode; wherein, the positive electrode comprises the conductive structure according to any one of claims 1 to 7.
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