CN113488616A - Negative electrode complex with high cycle performance, preparation method thereof and lithium metal battery - Google Patents
Negative electrode complex with high cycle performance, preparation method thereof and lithium metal battery Download PDFInfo
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Abstract
The invention discloses a negative electrode complex with high cycle performance, a preparation method thereof and a lithium metal battery. The negative electrode composite body comprises a base material layer and lithium metal layers located on the two side faces of the base material layer, the base material layer is composed of a polymer area and a welding area located on at least one side of the polymer area, the polymer area is provided with a polyolefin film, and the welding area is provided with a welding sheet. The prepared negative electrode complex can play a role of a negative electrode and a current collector, and meanwhile, the complex has high liquid absorption rate and can remarkably improve the electrolyte retention capacity of the battery, so that the battery capacity of the lithium metal battery is improved.
Description
Technical Field
The application relates to the field of lithium batteries, in particular to a negative electrode complex with high cycle performance, a preparation method thereof and a lithium metal battery.
Background
Lithium metal batteries include lithium ion batteries and lithium metal batteries, and since lithium metal batteries are likely to cause uneven lithium deposition on a negative electrode during charging, safety performance and cycle performance thereof are poor. Therefore, lithium ion batteries with stable performance and long cycle life are widely applied, and the related technology is mature. However, compared with the lithium ion battery, the lithium metal battery has higher energy density and much higher cruising ability than the lithium ion battery, so the lithium metal battery has great development potential.
In a lithium ion battery, carbon materials such as graphite are generally adopted as a negative electrode, and metal materials such as copper foil are adopted as a current collector; the lithium metal battery uses lithium metal as a negative electrode, and the lithium metal has high conductivity and certain mechanical properties, so the lithium metal can be used as a composite of the negative electrode and a current collector, and the energy density of the lithium battery is favorably improved.
However, compared with the graphite negative electrode, the liquid absorbing and retaining capacity of the lithium metal is extremely poor, which is not beneficial to improving the content of the electrolyte in the lithium metal battery, and the content of the electrolyte is insufficient, which affects the cycle life of the battery, so that the improvement of the liquid absorbing and retaining capacity of the lithium metal is beneficial to improving the cycle life of the battery.
Disclosure of Invention
The application provides a negative electrode complex with high cycle performance, a preparation method thereof and a lithium metal battery.
In a first aspect, the present application provides a high cycle performance negative electrode composite comprising a substrate layer and lithium metal layers on top and bottom surfaces of the substrate layer, the substrate layer consisting of a polymer region and a welding region on at least one side of the polymer region, the polymer region being provided with a polyolefin film, the welding region being provided with a welding sheet.
By adopting the technical scheme, the absorption of the polyolefin film on the electrolyte can obviously improve the electrolyte content in the lithium metal battery, and further improve the cycle life of the lithium metal battery. The reason for this may be that the liquid-absorbing ability of the polyolefin film is mainly due to its pore structure, has excellent electrolyte wettability, and can promote the complex to absorb and retain more electrolyte, thereby improving the cycle life of the lithium metal battery.
In addition, the polyolefin film has good flexibility and can generate unstable wrinkles when being used as a load layer of the lithium metal layer in the battery charging process, so that the compressive stress generated in the lithium deposition process is released, the uneven lithium deposition generated on the surface of the lithium metal is reduced, and the charging cycle performance of the lithium metal battery is improved.
Preferably, the polyolefin film is one of a PP film, a PE film and a PP/PE/PP composite film.
By adopting the technical scheme, the PP film, the PE film and the PP/PE/PP composite film have good high temperature resistance, liquid absorption and retention performance and certain viscosity, and are beneficial to coating a liquid absorption layer.
Preferably, the welding sheet is made of one of current collector materials such as copper foil, copper mesh and stainless steel mesh.
By adopting the technical scheme, metals such as copper, stainless steel or titanium and the like are arranged in the welding area, so that the welding of the complex current collector and the lug is realized on one hand; on the other hand, the reticular metal current collector materials such as the copper mesh, the stainless steel mesh or the titanium mesh are beneficial to reducing the diffusion resistance of the electrolyte, promoting the utilization of the electrolyte to active substances and further being beneficial to improving the cycle performance of the battery.
Preferably, one side of the welding sheet, which is far away from the polyolefin film, exceeds the side edge of the lithium metal layer by 40-50 mm, and the overlapping area of the welding sheet and the lithium metal layer accounts for 5-10% of the total area of the lithium metal.
By adopting the technical scheme, more than part of the negative electrode composite body is beneficial to ensuring the welding assembly of the negative electrode composite body and the electrode lug. The part overlapped with the lithium metal layer is beneficial to keeping the stable connection of the welding sheet and the lithium metal layer.
Preferably, the surface of the polyolefin film is provided with a liquid absorbing layer, and the liquid absorbing layer is prepared by coating and drying the following components in parts by weight:
polyvinylidene fluoride: 5-10 parts;
nano montmorillonite: 5-20 parts of a solvent;
80-200 parts of organic solvent.
By adopting the technical scheme, the polyvinylidene fluoride is matched with the nano montmorillonite, so that the liquid absorption layer is formed on the surface of the polyolefin film, and the liquid absorption amount of the negative electrode composite substrate is effectively improved. The reason for this is probably that the nano montmorillonite has better temperature resistance and chemical resistance and better tolerance to the electrolyte. Meanwhile, the nano montmorillonite has a layered structure, has a good adsorption effect on the electrolyte, and can effectively improve the electrolyte adsorption capacity of the cathode complex.
The polyvinylidene fluoride can play a role of a binder on one hand, and the nano montmorillonite is fixed on the surface of the polyolefin membrane, so that the liquid absorption layer is not easy to fall off; on the other hand, polyvinylidene fluoride has high electrolyte tolerance and temperature resistance after being formed into a film, and can be dissolved in an organic solvent, so that the film formation and firm adhesion of the liquid absorption layer in the battery are guaranteed, the liquid absorption layer is not easy to fall off, and the battery is convenient to process and use.
In addition, polyvinylidene fluoride is dissolved in an organic solvent, and the organic solvent is gradually volatilized in a film forming process, so that pores are formed on the surface of the liquid absorbing layer, and the liquid absorbing rate of the liquid absorbing layer is improved.
Preferably, the organic solvent is one of N-methyl pyrrolidone, acetone or chloroform.
By adopting the technical scheme, the liquid absorption rate of the liquid absorption layer is further improved, and the reason may be that the solvent promotes the pores formed on the surface of the liquid absorption layer in the volatilization process, so that the liquid absorption rate of the liquid absorption layer is improved. The N-methyl pyrrolidone is low in volatilization speed, so that pores on the surface of the liquid absorbing layer are distributed more uniformly, and the absorption and permeation of the electrolyte are facilitated.
Preferably, the weight ratio of the polyvinylidene fluoride to the nano montmorillonite is 1: 1.5.
By adopting the technical scheme, the prepared liquid absorption layer has more excellent electrolyte adsorption capacity. The reason for this is probably that both the nano-montmorillonite and the film-formed polyvinylidene fluoride have imbibing effect, and the mechanical property of the imbibing layer cannot be satisfied if the content of the polyvinylidene fluoride is too high, and the requirement of cohesiveness cannot be satisfied if the content of the polyvinylidene fluoride is too low.
Preferably, the liquid absorbing layer is prepared according to the following steps:
s1, dissolving polyvinylidene fluoride in an organic solvent according to parts by weight, then adding nano-montmorillonite, and fully mixing to prepare premixed slurry;
s2, performing ball milling on the premixed slurry for 3-4 hours to prepare coating slurry;
and S3, soaking the polyolefin film into the coating slurry, taking out the polyolefin film after 10-30S, and drying the polyolefin film at the temperature of 70-80 ℃ to obtain the polyolefin film with the liquid absorption layer.
By adopting the technical scheme, the polyolefin film with the liquid absorbing layer is prepared. The slurry is subjected to ball milling, so that the phenomena of caking of the adhesive and agglomeration of the nano montmorillonite can be effectively reduced, the formation of a more uniform liquid absorption layer is promoted, and the liquid absorption rate of the slurry is further improved.
In a second aspect, the present application provides a method for preparing a negative electrode composite with high cycle performance, comprising the operations of:
and placing the welding sheet and the polyolefin film in parallel to obtain a substrate layer, and then rolling the two lithium sheets on two sides of the substrate layer to obtain a lithium metal layer.
The cathode complex comprises a three-layer structure which is sequentially arranged from top to bottom, wherein the upper side and the lower side of the cathode complex are both lithium sheets, and the middle layer consists of a polyolefin film and a welding sheet which are positioned on the same plane. The preparation method can be realized by rolling the three-layer structure into a whole.
In a third aspect, the present application provides a lithium metal battery comprising the negative electrode composite described in any one of the above.
By adopting the technical scheme, the prepared lithium metal battery has higher cycle life.
In summary, the present application has the following beneficial effects:
1. the application the negative pole complex body, through increasing the imbibition layer, compensatied the problem that the imbibition of lithium metal negative pole to electrolyte liquid retention performance is not enough, improved the electrolyte liquid retention volume of negative pole to increase the electrolyte content in the lithium metal battery, and then improved battery cycle life.
2. According to the negative electrode complex, the polyolefin substrate is added between the lithium metal layers, so that the stress generated by deposition of lithium ions on the negative electrode is effectively and slowly released, and the formation of lithium dendrites is reduced, and the cycle performance of the battery is improved.
3. The application the negative pole complex body, adopt polyvinylidene fluoride and nanometer montmorillonite as the raw materials, not only improved imbibition efficiency, guaranteed the cohesive force between polyolefin membrane and imbibition layer and the lithium metal moreover, effectively prevented the action of droing between each layer.
4. The application the negative pole complex body, compare in the negative pole complex body that does not use the polyolefin membrane, can effectively prevent the fold that the lithium piece caused at the roll-in-process, ensure lithium surfacing, be favorable to improving battery cycle life.
Drawings
Fig. 1 is a side view of a negative electrode composite in example 1;
fig. 2 is a front view of the anode composite in example 1.
Description of reference numerals:
1. a negative electrode composite; 2. a substrate layer; 3. a lithium metal layer; 4. a polymer 5 region; 41. a polyolefin film; 5. a welding zone; 51. and welding the sheets.
Detailed Description
Examples
Example 1, negative electrode complex body of high cycle performance, as shown in fig. 1, 2, this negative electrode complex body includes the substrate layer and the lithium metal layer of laminating on the substrate layer both sides side, the substrate layer is by the polymer district with lie in polymer one side and with the parallel welding zone in polymer district constitute, be provided with the PP film (polyolefin film) in the polymer district, be provided with the welding sheet on the welding zone, the welding sheet is the copper mesh that the current collector material used in this embodiment, and the welding sheet keeps away from the side of polyolefin film and surpasss the lithium metal layer side 40mm, the partial area that welding sheet and lithium metal layer coincide accounts for 10% of lithium metal total area. The negative electrode complex is formed by rolling and compounding two layers of lithium sheets and a base material layer positioned between the two lithium sheets into a whole.
The PP film is characterized in that a liquid absorbing layer is arranged on the surface of the PP film, the selection and the corresponding dosage of each raw material component of the liquid absorbing layer are shown in Table 1, and the PP film is prepared according to the following steps:
s1, dissolving polyvinylidene fluoride in a solvent according to parts by weight, then adding nano-montmorillonite, and fully mixing to prepare a premixed slurry;
s2, performing ball milling on the premixed slurry for 4 hours at the rotating speed of 200rpm to prepare coating slurry;
and S3, soaking the polyolefin film into the coating slurry, taking out the polyolefin film after 30 seconds, and drying the polyolefin film at 70 ℃ to obtain the polyolefin film with the liquid absorption layer.
Example 2, negative electrode complex body of high cycle performance, as shown in fig. 1, 2, this negative electrode complex body includes the substrate layer and the lithium metal layer of laminating on the substrate layer both sides side, the substrate layer is distinguished and is located polymer one side and the zone of welding that is parallel with polymer, be provided with PP membrane (polyolefin membrane) in the polymer district, be provided with the welding sheet on the zone of welding, the welding sheet is the copper mesh that the current collector material used in this embodiment, and the welding sheet keeps away from the one side of polyolefin membrane (the side that is close to the battery utmost point ear) and surpasss lithium metal layer side 50mm, the partial area that welding sheet and lithium metal layer coincide accounts for 5% of the total area of lithium metal. The negative electrode complex is formed by rolling and compounding two layers of lithium sheets and a base material layer positioned between the two lithium sheets into a whole.
The PP film is characterized in that a liquid absorbing layer is arranged on the surface of the PP film, the selection and the corresponding dosage of each raw material component of the liquid absorbing layer are shown in Table 1, and the PP film is prepared according to the following steps:
s1, dissolving polyvinylidene fluoride in a solvent according to parts by weight, then adding nano-montmorillonite, and fully mixing to prepare a premixed slurry;
s2, performing ball milling on the premixed slurry for 3 hours at the rotating speed of 300rpm to prepare coating slurry;
and S3, soaking the polyolefin film into the coating slurry, taking out the polyolefin film after 10 seconds, and drying the polyolefin film at the temperature of 80 ℃ to obtain the polyolefin film with the liquid absorption layer.
Examples 3 to 9, negative electrode composites with high cycle performance, were different from example 1 in that the selection of each raw material component in the liquid absorbent layer and the corresponding amount thereof were as shown in table 1.
Table 1 example 1 to 9 raw material components and their respective amounts (kg) of the liquid absorbent layer in the negative electrode current collector
Example 10, a negative electrode composite with high cycle performance was different from example 1 in that no liquid absorbent layer was provided on the surface of the polyolefin film.
Example 11, a negative electrode composite with high cycle performance, was different from example 1 in that a PE film was used as the polyolefin film.
Example 12, a negative electrode composite with high cycle performance, is different from example 1 in that a PP/PE/PP composite film is used as a polyolefin film.
Example 13, a negative electrode composite with high cycle performance, differs from example 1 in that the land is a copper foil.
Example 14, a negative electrode composite with high cycle performance, differs from example 1 in that the weld zone is a stainless steel mesh.
Comparative example 1, a high cycle performance negative electrode composite, was different from example 1 in that the substrate layer of the negative electrode composite was not provided with a weld zone.
Comparative example 2, a negative electrode composite of high cycle performance, differs from example 1 in that the negative electrode composite consists of two rolled lithium metal layers without providing a substrate layer.
Application example
Application example 1, a lithium metal battery includes a positive electrode, a positive electrode current collector, a separator, and the negative electrode complex in example 1. The lithium metal battery is a soft package lithium metal battery, wherein the positive electrode material of the lithium metal battery is NCM811, and the electrolyte is 1M LiPF6the/EC-DEC (1:1 Vol%), separator was a conventional PP film, and the cell capacity was 1 Ah.
Application examples 2 to 14 are different from application example 1 in that the negative electrode composites of examples 2 to 15 are used.
Comparative example
Comparative examples 1 to 2 are lithium metal batteries different from application example 1 in that the negative electrode composites of comparative examples 1 to 2 were used.
Comparative example 3 is a lithium metal battery different from application example 1 in that lithium metal was used as a negative electrode and copper foil was used as a negative electrode current collector.
Performance test
Test 1: preparing an electrolyte adsorption amount test sample of the negative electrode complex: the negative electrode composites of examples 1 to 14 and comparative examples 1 to 2 were used as test samples.
The test method comprises the following steps: weighing dry cell with mass m0The mass of the soft package battery after the second sealing is m1The weight change Δ m before and after calculation, and the test results are shown in table 2.
Test 2: preparing a lithium metal battery cycle life test sample: the lithium metal batteries of application examples 1 to 14 and comparative examples 1 to 3 were used as test samples.
The test method comprises the following steps: the lithium metal battery was subjected to 0.2C/0.2C charge-discharge cycling until the capacity retention rate was 80%, the number of cycles of the battery was recorded, and the test results are shown in table 2.
TABLE 2 test results of test 1 and test 2
And (3) analyzing test results:
(1) as can be seen from the combination of application examples 1 to 14 and comparative examples 1 to 3 and the combination of table 2, the application examples 1 to 14 adopt the negative electrode composite body of the present application, and the negative electrode composite body adds the polyolefin film and the welding sheet between the lithium metal layers, thereby significantly increasing the electrolyte retention amount of the negative electrode composite body and improving the cycle life of the lithium metal battery. The reason for this may be that the liquid absorbing ability of the polyolefin film is mainly attributed to its pore structure, so that the negative electrode composite has excellent wettability with the electrolyte. Compared with current collectors such as copper foil and the like, the polyolefin film is used as the base material of the negative current collector, so that the composite body is promoted to absorb and retain more electrolyte, and the cycle life of the lithium metal battery is prolonged.
In addition, the polyolefin film has good flexibility and can generate unstable wrinkles when being used as a load layer of a lithium metal layer in the process of charging the battery, so that the compressive stress generated in the process of lithium deposition is released, the uneven lithium deposition generated on the surface of the lithium metal is reduced, the loss of active lithium is reduced, and the charging cycle performance of the lithium metal battery is improved.
(2) By combining application examples 1-2 with application examples 4-5 and combining table 2, it can be seen that compared with the liquid absorption layer of the negative electrode complex in application examples 1-2, polyvinylidene fluoride and nano-montmorillonite are matched together; the application examples 4 to 5 lack one component of the negative electrode composite, so that the electrolyte retention amount of the negative electrode composite in the application examples 1 to 2 and the cycle life of the lithium metal battery are superior to those of the application examples 4 to 5. The reason for this is probably that the nano-montmorillonite has a layered structure, and the interlayer thereof can adsorb the electrolyte, thereby increasing the electrolyte adsorption amount of the negative electrode complex.
On one hand, the polyvinylidene fluoride can play a role of a binder, and the nano montmorillonite is fixed on the surface of the polyolefin membrane, so that the liquid absorption layer is not easy to fall off; on the other hand, polyvinylidene fluoride is dissolved in an organic solvent, and the organic solvent is gradually volatilized in the film forming process, so that pores are formed on the surface of the liquid absorbent layer, and the increase of the liquid absorption rate of the liquid absorbent layer can be promoted.
(3) As can be seen by combining application examples 1 to 2 with application examples 6 to 7 and combining table 2, compared with the liquid absorption layer of the negative electrode complex in application examples 1 to 2, N-methylpyrrolidone is used as a solvent; in the application examples 4 to 5, acetone and chloroform are respectively used as solvents, so that the electrolyte retention capacity of the negative electrode complex and the cycle life of the lithium metal battery in the application examples 1 to 2 are superior to those in the application examples 6 to 7. The reason for this may be that the volatilization speed of acetone and chloroform is too fast, which causes the pore size and distribution of polyvinylidene fluoride formed after film formation to be uneven, which is not favorable for loading the electrolyte. The volatilization speed of the N-methyl pyrrolidone is moderate, so that the pore distribution on the surface of the liquid absorbing layer is more uniform, and the liquid absorbing and retaining performance of the liquid absorbing layer is favorably exerted.
Although preferred embodiments of the present invention have been described in detail hereinabove, it should be clearly understood that modifications and variations of the present invention are possible to those skilled in the art. 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 (10)
1. The negative electrode composite body with high cycle performance is characterized by comprising a substrate layer and lithium metal layers located on two side faces of the substrate layer, wherein the substrate layer is composed of a polymer area and a welding area located on at least one side of the polymer area, the polymer area is provided with a polyolefin film, and the welding area is provided with a welding sheet.
2. The negative electrode complex with high cycle performance according to claim 1, wherein the polyolefin film is one of a PP film, a PE film and a PP/PE/PP composite film.
3. The high cycle performance negative electrode composite as claimed in claim 1, wherein the welding sheet is made of one of current collector materials such as copper foil, copper mesh, stainless steel mesh, etc.
4. The high cycle performance negative electrode composite as claimed in claim 1, wherein the side of the welding sheet facing away from the polyolefin film exceeds the side of the lithium metal layer by 40-50 mm, and the overlapping area of the welding sheet and the lithium metal layer accounts for 5-10% of the total area of the lithium metal.
5. The high cycle performance negative electrode composite according to claim 1, wherein the polyolefin film is provided with a liquid absorbent layer on the surface thereof, and the liquid absorbent layer is prepared by coating and drying the following components in parts by weight:
polyvinylidene fluoride: 5-10 parts;
nano montmorillonite: 5-20 parts of a solvent;
80-200 parts of organic solvent.
6. The negative electrode composite with high cycle performance according to claim 5, wherein the organic solvent is one of N-methylpyrrolidone, acetone, and chloroform.
7. The negative electrode composite with high cycle performance as claimed in claim 5, wherein the weight ratio of the polyvinylidene fluoride to the nano montmorillonite is 1: 1.5.
8. The high cycle performance negative electrode composite according to claim 5, wherein the liquid absorbent layer is prepared by the following steps:
s1, dissolving polyvinylidene fluoride in an organic solvent according to parts by weight, then adding nano-montmorillonite, and fully mixing to prepare premixed slurry;
s2, performing ball milling on the premixed slurry for 3-4 hours to prepare coating slurry;
and S3, soaking the polyolefin film into the coating slurry, taking out the polyolefin film after 10-30S, and drying the polyolefin film at the temperature of 70-80 ℃ to obtain the polyolefin film with the liquid absorption layer.
9. The method for producing a negative electrode composite with high cycle performance according to any one of claims 1 to 8, comprising the steps of:
and arranging the welding sheet and the polyolefin film in parallel on the same horizontal plane to obtain a substrate layer, and rolling two lithium sheets on two sides of the substrate layer to obtain lithium metal layers to obtain the cathode composite.
10. A lithium metal battery comprising the negative electrode composite according to any one of claims 1 to 9.
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| CN102347475A (en) * | 2010-07-27 | 2012-02-08 | 曾永斌 | High-performance lithium ion battery and preparation process thereof |
| CN107305950A (en) * | 2016-04-19 | 2017-10-31 | 宁德新能源科技有限公司 | Polymeric protective film, lithium anode piece, lithium secondary battery |
| CN106784600A (en) * | 2016-12-23 | 2017-05-31 | 天津力神电池股份有限公司 | One kind is containing lithium cathode sheet and preparation method thereof |
| CN206878100U (en) * | 2017-05-09 | 2018-01-12 | 宁德时代新能源科技股份有限公司 | collector and electrochemical energy storage device |
| US20200274146A1 (en) * | 2017-12-04 | 2020-08-27 | Lg Chem, Ltd. | Lithium electrode, method for manufacturing same, and lithium secondary battery comprising same |
| CN208385526U (en) * | 2018-07-06 | 2019-01-15 | 珠海光宇电池有限公司 | A kind of lithium battery cathode plate and lithium battery |
| CN209001017U (en) * | 2018-08-20 | 2019-06-18 | 珠海光宇电池有限公司 | Lithium secondary battery anode piece and lithium secondary battery |
| CN110289382A (en) * | 2019-07-23 | 2019-09-27 | 深圳锂硫科技有限公司 | A kind of preparation method and lithium battery diaphragm of lithium battery diaphragm |
| CN110797506A (en) * | 2019-10-10 | 2020-02-14 | 武汉瑞科美新能源有限责任公司 | Composite lithium metal negative electrode material, preparation method and application thereof, and lithium metal battery |
| CN111370752A (en) * | 2020-04-08 | 2020-07-03 | 隆能科技(南通)有限公司 | Fast charging and safe low temperature lithium ion battery and method of manufacturing the same |
| CN112889164A (en) * | 2020-04-23 | 2021-06-01 | 宁德时代新能源科技股份有限公司 | Lithium metal battery, preparation method thereof, device containing lithium metal battery and negative pole piece |
| CN112216811A (en) * | 2020-09-23 | 2021-01-12 | 电子科技大学 | Preparation method of ultrathin lithium metal cathode |
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