CN216928627U - Lithium-copper composite belt, lithium-copper composite negative electrode and battery - Google Patents
Lithium-copper composite belt, lithium-copper composite negative electrode and battery Download PDFInfo
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- CN216928627U CN216928627U CN202220541614.0U CN202220541614U CN216928627U CN 216928627 U CN216928627 U CN 216928627U CN 202220541614 U CN202220541614 U CN 202220541614U CN 216928627 U CN216928627 U CN 216928627U
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Abstract
The utility model provides a lithium-copper composite belt, a lithium-copper composite cathode and a battery. The lithium copper composite tape has: a copper foil having a width of 20-400mm and a thickness of 3-20 μm; and a plurality of ultra-thin lithium foils on at least one surface of the copper foil, each of the ultra-thin lithium foils having a width identical to that of the copper foil, each of the ultra-thin lithium foils having a thickness identical to that of the copper foil within a range of 0.5 to 50 μm, and adjacent ultra-thin lithium foils having a spacing identical to a distance in a length direction.
Description
Technical Field
The utility model relates to the technical field of energy storage, in particular to a lithium-copper composite belt and a lithium-copper composite cathode which can be used for a secondary battery and a solid-state battery.
Background
At present, lithium batteries are used as main energy storage devices, and the lithium batteries are not only widely applied to portable electronic products but also widely applied to the automobile industry due to high working voltage, good cycle performance, high energy density and power density and environmental friendliness, and with the research and development of high-end battery products and the increase of automobile endurance mileage, the negative electrode material graphite of lithium ion batteries used in batches at present reaches the theoretical limit value (372mAh/g), new materials are urgently needed to be developed, and the metal lithium has high capacity (theoretical 3860mAh/g) and low density (0.534 g/cm/g)3) Since the electrochemical potential is low (-3.040V vs. standard hydrogen electrode), lithium metal secondary batteries using lithium metal as a negative electrode, such as lithium sulfur batteries, lithium air batteries, lithium intercalation compound batteries, and the like, have the advantages of high energy density, high voltage, and the like, and are also the current trend in the research of high energy density batteries.
Lithium metal is generally required to have a large width when used in secondary batteries and solid-state batteries, particularly, lithium copper composite tapes using copper foil as a current collector are used in large-sized batteries. The conventional production process is to continuously compound the lithium metal foil and the copper foil, and reserve a tab in the width direction, so that the copper foil covered by the lithium metal foil is rolled and extended during compounding, and the copper foil at the tab part is not rolled because the copper foil is not covered by the lithium metal foil and has a thinner total thickness, so that the lithium-copper composite strip has a larger wrinkle at the tab during production, and the production and the battery performance of the subsequent process of the battery are influenced. And because the width of the current metal lithium foil is limited, only a lithium copper composite belt with a narrow width can be produced by adopting the conventional process, and the requirement of a large-size battery cannot be met.
SUMMERY OF THE UTILITY MODEL
In view of these problems, the present invention provides a copper foil/ultra-thin lithium foil composite strip having ultra-thin lithium foils laminated at intervals in a length direction, the ultra-thin lithium foils having the same width as that of the copper foils, the intervals provided in the length direction (copper foil portions where the ultra-thin lithium foils are not laminated) being used as tabs of a battery, and the lithium copper composite portions between adjacent intervals having an arbitrary length, so that the lithium copper composite strip or the lithium copper composite negative electrode of the present invention can be applied to a large-sized lithium battery, such as a blade battery. In addition, the copper foil is completely covered by the metal lithium foil in the production process, all parts of the copper foil are rolled to the same degree, and no wrinkle is generated.
One aspect of the present invention is directed to a lithium copper composite tape having: a copper foil having a width of 20-400mm and a thickness of 3-20 μm; and a plurality of ultra-thin lithium foils disposed on at least one surface of the copper foil and laminated with the copper foil, each of the ultra-thin lithium foils having a width identical to that of the copper foil, each of the ultra-thin lithium foils having a thickness identical to that of the copper foil within a range of 0.5 to 50 μm, and adjacent ultra-thin lithium foils having a distance identical therebetween in a length direction.
The lithium copper composite strip is a composite strip formed by compounding a plurality of ultrathin lithium foils on a copper foil at intervals along the length direction, and the width, the thickness and the length of each ultrathin lithium foil are adjustable.
In the present invention, the ultra-thin lithium foil is a uniform thin film, which means that the ultra-thin lithium foil has a complete thin film shape (without significant wrinkles and deformations) and has a uniform thickness. Preferably, the ultra-thin lithium foil has relatively uniform through-holes throughout the lithium film.
Optionally, the ultra-thin lithium foil on the lithium copper composite tape satisfies at least one of the following conditions:
the ultrathin lithium foil is provided with a through hole, and the aperture of the through hole is 100-500 microns;
porosity of 0.1-10%, preferably 1-5%;
the width is 20-400 mm;
the length is 50-2000 mm;
the thickness is 1-20 μm, preferably 1-10 μm, and the thickness tolerance is + -1 μm;
the distance between adjacent ultrathin lithium foils is 5-200 mm.
Optionally, the surface of the ultrathin lithium foil is bright and is silvery white, the lithium content is 99.90-99.95%, the thickness range of the lithium film is 0.5-50 micrometers, preferably 1-10 micrometers, and the thickness tolerance is +/-1 micrometer.
Optionally, the ultra-thin lithium foil is a metallic lithium alloy article, the lithium alloy is an alloy of lithium and at least one of silicon, magnesium, aluminum, indium, boron, tin, gallium, yttrium, silver, copper, lead, bismuth, sodium, carbon, germanium, titanium, chromium, cobalt, tungsten, iron, niobium, nickel, gold, barium, cadmium, cesium, calcium, manganese, nitrogen, platinum, sulfur, thallium, strontium, tellurium, zinc, antimony, and zirconium, and the lithium content is 10-99.9%.
Optionally, the lithium copper composite tape is rolled.
The utility model also provides a lithium-copper composite negative electrode, wherein the lithium-copper composite negative electrode is a part of the lithium-copper composite belt, and the part is obtained by cutting the lithium-copper composite belt from a gap.
Optionally, the lithium copper composite anode comprises: copper foil; and an ultra-thin lithium foil on at least one surface of the copper foil; the width of the ultrathin lithium foil is the same as that of the copper foil, the length of the ultrathin lithium foil is smaller than that of the copper foil, and the ultrathin lithium foil is positioned on one side of the copper foil or in the middle of the copper foil in the length direction.
Another aspect of the present invention provides a battery comprising a positive electrode and a negative electrode oppositely disposed, wherein the negative electrode comprises the above-mentioned lithium copper composite tape or lithium copper composite negative electrode.
Optionally, the battery comprises a lithium metal battery, an all-solid-state battery, a lithium sulfur battery, or a lithium air battery.
According to the utility model, the copper foil interval is reserved in the length direction to be used as the tab, so that the ultra-thin lithium foil and the copper foil of the lithium-copper composite belt are the same in width in the width direction, and the problem of wrinkling caused by uneven rolling stress in the production process is avoided; meanwhile, the size of the ultrathin lithium foil can be freely controlled in the length direction, so that the product can be applied to large-size batteries.
Drawings
Fig. 1 is a schematic view of a single-sided lithium copper composite tape of the present invention.
Fig. 2 is a schematic view of a double-sided lithium copper composite tape according to the present invention.
Fig. 3 is a schematic diagram of a single-sided lithium copper composite negative electrode of the utility model.
Fig. 4 is a schematic diagram of a double-sided lithium copper composite negative electrode of the utility model.
FIG. 5 is a schematic diagram of a single-sided lithium copper composite tape preparation process in the utility model.
FIG. 6 is a schematic diagram of a double-sided lithium copper composite tape manufacturing process according to the present invention.
Description of the figure numbers:
a1 single-sided lithium-copper composite belt A11 single-sided lithium-copper composite negative electrode A2 double-sided lithium-copper composite belt
A21 double-sided lithium copper composite negative electrode 10 copper foil 20 first lithium foil strip
21 first lithium foil 22 first support film
30 second lithium foil strip 31 second lithium foil 32 second support film
40 roll device 51 upper side coating head 52 lower side coating head
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the utility model and are not intended to limit the utility model.
The lithium copper composite tape is divided into a single-sided lithium copper composite A1 and a double-sided lithium copper composite tape A2 according to the form of single-sided lithium composite or double-sided lithium composite of the copper foil.
Fig. 1 shows a schematic view of a single-sided lithium copper composite tape a1 of the present invention. As shown in fig. 1, the width of the first lithium foil 21 of the single-sided lithium copper composite tape a1 in the tape width direction is the same as the width of the copper foil 10, the first lithium foil 21 is in a block shape with the same size in the length direction, an uncovered exposed copper foil 10 is arranged between two adjacent lithium foils, and the copper foils at the exposed part have the same width and length.
Fig. 2 shows a schematic view of a double-sided lithium copper composite tape a2 of the present invention. As shown in fig. 2, the width of the first lithium foil 21 and the width of the second lithium foil 31 of the double-sided lithium copper composite tape a2 are the same as the width of the copper foil 10 in the tape width direction, the first lithium foil 21 and the second lithium foil 31 are in the shape of blocks with the same size in the length direction, an uncovered exposed copper foil 10 is arranged between two adjacent lithium foils on the same surface of the copper foil, and the copper foils on the exposed part have the same width and length.
Fig. 3 shows an embodiment of the single-sided lithium copper composite negative electrode a11 according to the present invention, wherein the single-sided lithium copper composite negative electrode a11 is composed of a copper foil 10 and a first lithium foil 21 laminated on the copper foil 10, the width of the first lithium foil 21 is the same as the width of the copper foil 10, and the length of the first lithium foil 21 is smaller than the length of the copper foil 10. In the embodiment, one side of the first lithium foil 21 in the length direction is aligned with the edge of the copper foil 10, and the other side is a bare copper foil; in other embodiments, the first lithium foil 21 may be located at the center of the copper foil 10 in the length direction, with both sides having bare copper foils. The single-sided lithium copper composite negative electrode a11 can be obtained from the single-sided lithium copper composite tape a1 of the present invention by cutting (die cutting, laser cutting, knife cutting, shearing, etc.).
Fig. 4 shows an embodiment of the double-sided lithium copper composite negative electrode a21 according to the present invention, wherein the double-sided lithium copper composite negative electrode a21 is composed of a copper foil 10 and a first lithium foil 21 and a second lithium foil 31 laminated on the copper foil 10, the first lithium foil 21 and the second lithium foil 31 have the same width as the copper foil 10, and the first lithium foil 21 and the second lithium foil 31 have a length smaller than the copper foil 10. In the embodiment, one side of the first lithium foil 21 and one side of the second lithium foil 31 in the length direction are aligned with the edge of the copper foil 10, and the other side is a bare copper foil; in other embodiments, the first and second lithium foils 21 and 31 may be located at the center of the copper foil 10 in the length direction, with both sides having bare copper foils. The double-sided lithium copper composite negative electrode a21 can be obtained from the double-sided lithium copper composite tape a2 of the present invention by cutting (die cutting, laser cutting, knife cutting, shearing, etc.).
The lithium-copper composite tape can be prepared by a roll-to-roll continuous production method, and comprises the following specific steps:
s1: providing an ultra-thin lithium foil strip having a thickness of 0.5 to 50 μm supported by a support layer;
s2: providing a copper foil with the thickness of 3-15 mu m;
s3: carrying out lithiation-philic treatment on the copper foil;
s4: coating a release agent on the part of the copper foil or the ultrathin lithium foil strip;
s5: after being attached, the copper foil and the ultrathin lithium foil strip enter a rolling device together;
s6: and peeling the supporting layer and the copper foil after rolling to obtain the lithium-copper composite belt.
Optionally, the ultra-thin lithium layer and the support layer on the ultra-thin lithium foil strip have a peel force of less than 100 gf.
Optionally, the lithiophilizing treatment of the copper foil is at least one of:
baking at 40-180 deg.C;
vacuum treatment is carried out, the vacuum degree is less than 100Pa, and the time is 0.5-48 h;
plasma treatment, wherein the treatment gas is one of argon, oxygen, nitrogen, argon-hydrogen mixed gas, compressed air and air;
roughening treatment, physical treatment (e.g., sanding) or chemical treatment;
optionally, the release agent is a high molecular polymer, such as polyvinyl alcohol, silicone oil, silicone grease, or emulsified paraffin.
The lithium copper composite negative electrode can be obtained by cutting a lithium copper composite belt from the interval of adjacent blocky ultrathin lithium foils through a cutting method.
Optionally, the cutting method comprises die cutting, laser cutting, knife cutting and shearing.
Example 1: preparation of Single-sided lithium copper composite tape A1
S1: providing a first lithium foil tape 20 having a lithium foil thickness of 5 μm, the first lithium foil tape 20 comprising a first support film 22 and a first lithium foil 21 attached to the first support film 22, and a peeling force when peeling the first lithium foil 21 from the first support film 22 being less than 50 gf; the widths of the first support film 22 and the first lithium foil 21 are both 150mm, that is, the width of the first lithium film 20 is 150 mm;
s2: providing a copper foil 10 with a thickness of 6 μm, the copper foil 10 having a width of 150 mm;
s3: carrying out vacuum treatment and baking treatment on the copper foil at the same time, wherein the vacuum degree is less than 100Pa, the baking temperature is 50-80 ℃, and the treatment time is 5 h;
s4: referring to fig. 5, a release agent is coated on a portion of the copper foil 10 using an upper side coating head 51;
s5: feeding the copper foil 10 and the first lithium foil strip 20 together into a rolling device 40 for rolling;
s6: peeling the first support film 22 from the copper foil 10 after rolling; the first lithium foil 21 corresponding to the portion of the copper foil 10 coated with the release agent is not combined with the copper foil 10 and remains on the first support film 22; the first lithium foil 21 corresponding to the part of the copper foil 10 not coated with the release agent has been peeled from the first support film 22 and is laminated to the copper foil 10, thereby obtaining a single-sided lithium-copper composite tape a1 as shown in fig. 1.
Example 2: preparation of double-sided lithium copper composite tape A2
S1: providing a first lithium foil tape 20 and a second lithium foil tape 30 having a lithium foil thickness of 5 μm, the first lithium foil tape 20 comprising a first support film 22 and a first lithium foil 21 attached to the first support film 22, and a peeling force when peeling the first lithium foil 21 from the first support film 22 being less than 50 gf; the widths of the first support film 22 and the first lithium foil 21 are both 150mm, that is, the width of the first lithium film 20 is 150 mm; the second lithium foil strip 30 is identical to the first lithium foil strip 20, and "first" and "second" are used herein only for ease of description of the intent and understanding of the present invention.
S2: providing a copper foil 10 with a thickness of 6 μm, the copper foil 10 having a width of 150 mm;
s3: carrying out vacuum treatment and baking treatment on the copper foil at the same time, wherein the vacuum degree is less than 100Pa, the baking temperature is 50-80 ℃, and the treatment time is 5 h;
s4: referring to fig. 6, an upper surface and a lower surface of a copper foil 10 are simultaneously coated with a release agent using an upper side coating head 51 and a lower side coating head 52 at portions of the copper foil 10;
s5: feeding the first lithium foil strip 20, the second lithium foil strip 30 and the copper foil 10 together into a rolling device 40 for rolling;
s6: peeling the first support film 22 and the second support film 32 from the copper foil 10 after rolling; the first lithium foil 21 and the second lithium foil 31 corresponding to the release agent coated portion on the copper foil 10 are not combined with the copper foil 10 and remain on the first support film 22 and the second support film 32, respectively; the first lithium foil 21 and the second lithium foil 31 at the corresponding parts of the copper foil 10 where the release agent is not coated have been peeled off from the first support film 22 and the second support film 32, respectively, and are laminated to the copper foil 10, thereby obtaining a double-sided lithium copper composite tape a2 as shown in fig. 2.
It should be understood that the above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A lithium copper composite strip, characterized in that the composite strip has:
a copper foil having a width of 20-400mm and a thickness of 3-20 μm; and
and a plurality of ultra-thin lithium foils on at least one surface of the copper foil, each of the ultra-thin lithium foils having the same width as the copper foil, each of the ultra-thin lithium foils having a uniform thickness within a range of 0.5 to 50 μm, and adjacent ultra-thin lithium foils having a same distance therebetween in a length direction.
2. The lithium-copper composite tape according to claim 1, wherein: the ultra-thin lithium foil satisfies at least one of the following conditions:
the ultrathin lithium foil is provided with a through hole, and the aperture of the through hole is 100-500 microns;
porosity is 0.1-10%;
the length is 50-2000 mm.
3. The lithium-copper composite tape according to claim 1, wherein: the spacing between adjacent ultrathin lithium foils is 5-200 mm.
4. The lithium-copper composite tape according to claim 1, wherein: the lithium copper composite tape is rolled.
5. A lithium copper composite negative electrode, characterized in that the lithium copper composite negative electrode is a portion of the lithium copper composite tape according to any one of claims 1 to 4, which is obtained by cutting the lithium copper composite tape from a space.
6. The lithium-copper composite negative electrode according to claim 5, wherein the lithium-copper composite negative electrode comprises a copper foil and an ultra-thin lithium foil on at least one surface of the copper foil, the ultra-thin lithium foil having the same width as the copper foil, the ultra-thin lithium foil having a length smaller than the copper foil, the ultra-thin lithium foil being located on one side of the copper foil or in the middle of the copper foil in a length direction.
7. A battery comprising a positive electrode and a negative electrode disposed opposite to each other, wherein the negative electrode comprises the lithium copper composite tape according to any one of claims 1 to 4 or the lithium copper composite negative electrode according to any one of claims 5 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202220541614.0U CN216928627U (en) | 2022-03-14 | 2022-03-14 | Lithium-copper composite belt, lithium-copper composite negative electrode and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202220541614.0U CN216928627U (en) | 2022-03-14 | 2022-03-14 | Lithium-copper composite belt, lithium-copper composite negative electrode and battery |
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| Publication Number | Publication Date |
|---|---|
| CN216928627U true CN216928627U (en) | 2022-07-08 |
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| CN202220541614.0U Active CN216928627U (en) | 2022-03-14 | 2022-03-14 | Lithium-copper composite belt, lithium-copper composite negative electrode and battery |
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- 2022-03-14 CN CN202220541614.0U patent/CN216928627U/en active Active
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