Electrode slurry for use in electrochemical energy storage device

Abstract

To provide a novel electrode slurry for use in an electrochemical energy storage device, which can efficiently control residual alkali and its side reactions in a positive electrode active material and has good viscosity characteristics.SOLUTION: The present invention provides an electrode slurry for use in an electrochemical energy storage device, which contains one or more compounds or polymers that form a stable structure represented by the formula (I), and X stabilizes the structure of the formula (I) by resonating with the following formula.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an electrode slurry used in an electrochemical energy storage device, and particularly includes one or more compounds or polymers that form a stable structure represented by formula (I), TIFF2025096178000001.tif7170 wherein X is TIFF2025096178000002.tif6170 which resonates to stabilize the structure of formula (I), and relates to an electrode slurry used in an electrochemical energy storage device.

Background Art

[0002] Electrochemical energy storage devices are widely applied to various electrical products. The physical and chemical properties of the electrode slurry used in an electrochemical energy storage device have a certain influence on the charge and discharge characteristics of the electrochemical energy storage device. In particular, the viscosity of the electrode slurry and its change over time significantly affect the difficulty of the manufacturing process of the electrochemical energy storage device, the yield rate of the product, and the service life.

[0003] In the prior art, compounds or polymers have been added to improve the viscosity characteristics of the electrode slurry used in an electrochemical energy storage device. However, there is still room for improvement in the adjustment of the viscosity of the electrode slurry used in the electrochemical energy storage device in the prior art.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, an object of the present invention is to provide a novel electrode slurry used in an electrochemical energy storage device that can efficiently control the residual alkali of the positive electrode active material and its side reactions, and further has good viscosity characteristics.

Means for Solving the Problems

[0005] To achieve the above object and other objects, the present invention includes one or more compounds or polymers that form a stable structure represented by formula (I), TIFF2025096178000003.tif7170 wherein X is, TIFF2025096178000004.tif6170 By resonating with, provide an electrode slurry for an electrochemical energy storage device that stabilizes the structure of the formula (I).

[0006] In the electrode slurry, X is, TIFF2025096178000005.tif21170 selected from the organic moiety of, R1 and R2 are substituents selected from the group consisting of linear or cyclic alkyl groups, aryl groups, and derivatives thereof, R is a substituent selected from the group consisting of alkyl groups, carboxyl groups, carbonyl groups, hydroxyl groups, and derivatives thereof.

[0007] The electrode slurry further contains lithium, sodium, or a compound thereof.

[0008] The electrode slurry further contains a polymer or copolymer derived from monomers of vinylidene fluoride (VDF) and / or acrylonitrile (AN).

[0009] In the electrode slurry, the copolymer has the following structure, TIFF2025096178000006.tif81170 wherein G I is derived from acrylonitrile, wherein G II is derived from acrylate or methacrylate, and R4 is a linear alkyl group, wherein G III is derived from a vinyl lactam-based compound, and A is a cyclic amide group, wherein G IVIt is derived from acrylic acid or methacrylic acid, said R3 is H or CH3, The quantity of the constituent repeating units of the copolymer satisfies the following formula. TIFF2025096178000007.tif10170

[0010] In the electrode slurry, in the copolymer, said G I is 50 to 98% by weight, said G II is 0.5 to 20% by weight, said G III is 0.5 to 20% by weight, said G IV is 0.5 to 20% by weight.

[0011] In the electrode slurry, the compound or polymer with respect to the total solid content of the electrode slurry is 0.001 to 10% by weight.

[0012] In the electrode slurry, the compound containing oxygen, nitrogen, or sulfur may be selected from the group consisting of, but not limited to, aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, butyral, cinnamaldehyde, glucose, benzaldehyde, etc.; piperidine or pyrrolidine compounds such as tetrahydropyrrole, pyrroline, pyrrole, hexahydropiperidine, tetramethylpiperidine oxide, N-methylpiperidine-2-ethanol, R-3-aminopiperidine hydrochloride, etc.; phenolic compounds such as phenol, polyphenol, hydroquinone, bisphenol A, dibutylhydroxytoluene, 2-methylphenol, 2-isopropyl-5-methylphenol, hindered phenol, xylenol, hydroquinone monomethyl ether, propofol, nonylphenol, cresol, salicylic acid, methyl salicylate, phenolic resin, and their derivatives, etc.; nitrile compounds such as methylnitrile, acetonitrile, hydrogen cyanide, cyanic acid, cyanuric acid, thiocyanic acid, malononitrile, succinonitrile, acrylonitrile, vitamin B12, potassium ferricyanide, potassium nickel cyanide, potassium cobalt cyanide, Prussian blue, potassium silver cyanide, potassium gold cyanide, potassium cyanide, sodium cyanide, zinc cyanide, silver cyanide, cuprous cyanide, mercury cyanide, nickel cyanide, cobalt cyanide, polyacrylonitrile, etc.; and ketone compounds such as aliphatic ketones, alicyclic ketones, aromatic ketones, acetone, butanone, methyl ethyl ketone, cyclohexanone, butanedione, acetoacetone, etc.

[0013] In the electrode slurry, the compound or polymer is selected from the group consisting of compounds containing a phenolic moiety, compounds containing an aminoxide moiety, phenols, and their derivatives or derivative polymers.

[0014] In the electrode slurry, the compound or polymer is selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy, tetramethylpiperidinyloxy, phenol, polyphenol, hydroquinone, hydroquinone monomethyl ether, and derivatives or derivative polymers thereof. [Advantages of the Invention]

[0015] The electrode slurry used in the electrochemical energy storage device according to the present invention has more suitable viscosity characteristics compared to the prior art. [Embodiments for Carrying Out the Invention]

[0016] Hereinafter, in order to fully explain the object, features, and effects of the present invention, the present invention will be described in more detail using the following specific examples.

[0017] [Example 1] A polyacrylonitrile copolymer as an anti-gelation additive, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a phenol additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:10, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using N-methylpyrrolidone (NMP) as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0018] Here, the phenol additive can form a stable structure represented by the following formula (I). TIFF2025096178000008.tif7170X is By resonating with TIFF2025096178000009.tif6170, the structure of formula (I) is stabilized.

[0019] [Example 2] A polyacrylonitrile copolymer as a gelation inhibitor, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a phenolic additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:20, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using N-methylpyrrolidone (NMP) as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0020] Here, the phenolic additive can form a stable structure represented by the following formula (I). TIFF2025096178000010.tif7170X By resonating with TIFF2025096178000011.tif6170, the structure of formula (I) is stabilized.

[0021] [Example 3] A polyacrylonitrile copolymer as a gelation inhibitor, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a piperidine additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:10, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0022] Here, the piperidine additive can form a stable structure represented by the following formula (I). TIFF2025096178000012.tif7170X By resonating with TIFF2025096178000013.tif6170, the structure of formula (I) is stabilized.

[0023] [Example 4] A polyacrylonitrile copolymer used as an anti-gelling additive, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a piperidine additive used as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:20, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0024] Here, the piperidine additive can form a stable structure represented by the following formula (I). TIFF2025096178000014.tif7170X resonates with TIFF2025096178000015.tif6170 to stabilize the structure of formula (I).

[0025] [Example 5] A polyacrylonitrile copolymer used as an anti-gelling additive, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a hindered phenol additive used as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:10, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0026] Here, the hindered phenol additive can form a stable structure represented by the following formula (I). TIFF2025096178000016.tif7170X resonates with TIFF2025096178000017.tif6170 to stabilize the structure of formula (I).

[0027] [Example 6] A polyacrylonitrile copolymer used as an anti-gelation additive, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a hindered phenol additive used as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:20, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0028] Here, the hindered phenol additive can form a stable structure represented by the following formula (I). TIFF2025096178000018.tif7170X By resonating with TIFF2025096178000019.tif6170, the structure of formula (I) is stabilized.

[0029] [Example 7] A commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a piperidine additive are mixed at a weight ratio of 3.6:4:92:0.4, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0030] Here, the piperidine additive can form a stable structure represented by the following formula (I). TIFF2025096178000020.tif7170X By resonating with TIFF2025096178000021.tif6170, the structure of formula (I) is stabilized.

[0031] [Example 8] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and a hindered phenol additive are mixed at a weight ratio of 3.6:4:92:0.4, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The slurry after mixing is allowed to stand, and the change in its viscosity over time is observed.

[0032] Here, the hindered phenol additive can form a stable structure represented by the following formula (I). TIFF2025096178000022.tif7170X By resonating with TIFF2025096178000023.tif6170, the structure of formula (I) is stabilized.

[0033] [Example 9] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and a piperidine additive are mixed at a weight ratio of 3.2:4:92:0.8, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The slurry after mixing is allowed to stand, and the change in its viscosity over time is observed.

[0034] Here, the piperidine additive can form a stable structure represented by the following formula (I). TIFF2025096178000024.tif7170X By resonating with TIFF2025096178000025.tif6170, the structure of formula (I) is stabilized.

[0035] [Example 10] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and a hindered phenol additive are mixed at a weight ratio of 3.2:4:92:0.8, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0036] Here, the hindered phenol additive can form a stable structure represented by the following formula (I). TIFF2025096178000026.tif7170X By resonating with TIFF2025096178000027.tif6170, the structure of formula (I) is stabilized.

[0037] [Example 11] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and a benzenediol additive are mixed at a weight ratio of 3.6:4:92:0.4, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0038] Here, the benzenediol additive can form a stable structure represented by the following formula (I). TIFF2025096178000028.tif7170X By resonating with TIFF2025096178000029.tif6170, the structure of formula (I) is stabilized.

[0039] [Example 12] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and a benzenediol additive are mixed at a weight ratio of 3.2:4:92:0.8, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0040] Here, the benzenediol additive can form a stable structure represented by the following formula (I). TIFF2025096178000030.tif7170 is By resonating with TIFF2025096178000031.tif6170, the structure of formula (I) is stabilized.

[0041] [Comparative Example 1] A polyacrylonitrile copolymer as an anti-gelation additive, a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and an aldehyde-based additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:10, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0042] The aldehyde-based additive used in Comparative Example 1 cannot form a stable structure represented by the following formula (I) with respect to Examples 1 to 12. TIFF2025096178000032.tif7170

[0043] [Comparative Example 2] A polyacrylonitrile copolymer as a gelation inhibitor, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and an aldehyde-based additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:20, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The slurry after mixing is allowed to stand, and the change in its viscosity over time is observed.

[0044] The aldehyde-based additive used in Comparative Example 2 cannot form a stable structure represented by the following formula (I) with respect to Examples 1 to 12. TIFF2025096178000033.tif7170

[0045] [Comparative Example 3] A polyacrylonitrile copolymer as a gelation inhibitor, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a ketone-based additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:10, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The slurry after mixing is allowed to stand, and the change in its viscosity over time is observed.

[0046] The ketone-based additive used in Comparative Example 3 cannot form a stable structure represented by the following formula (I) with respect to Examples 1 to 12. TIFF2025096178000034.tif7170

[0047] [Comparative Example 4] A polyacrylonitrile copolymer as a gelation-preventing additive, a commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and a ketone-based additive as an auxiliary agent are mixed at a weight ratio of 0.8:3.2:4:92:80, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0048] The ketone-based additive used in Comparative Example 4 cannot form a stable structure represented by the following formula (I) with respect to Examples 1 to 12. TIFF2025096178000035.tif7170

[0049] [Comparative Example 5] A polyacrylonitrile copolymer as an adhesive, commercial carbon powder (Super P), and a commercial sodium cathode material (AMANDARRY Co., A107S) are mixed at a weight ratio of 4:4:92, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0050] In Comparative Example 5, an additive that can form a stable structure represented by the following formula (I) is not added with respect to Examples 1 to 12. TIFF2025096178000036.tif7170

[0051] [Comparative Example 6] A commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), a commercial sodium cathode material (AMANDARRY Co., A107S), and an aldehyde-based additive are mixed at a weight ratio of 3.6:4:92:0.4, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0052] The aldehyde-based additive used in Comparative Example 6 cannot form a stable structure represented by the following formula (I) with respect to Examples 1 to 12. TIFF2025096178000037.tif7170

[0053] [Comparative Example 7] A commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY Co., A107S), and an aldehyde-based additive are mixed at a weight ratio of 3.2:4:92:0.8, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0054] The aldehyde-based additive used in Comparative Example 7 cannot form a stable structure represented by the following formula (I) with respect to Examples 1 to 12. TIFF2025096178000038.tif7170

[0055] [Comparative Example 8] A commercial adhesive (Solvay Co., Ltd., 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY Co., A107S), and polyacrylonitrile (PAN) are mixed at a weight ratio of 3.6:4:92:0.4, and stirred for 30 minutes by a rotary defoamer (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0056] In Comparative Example 8, an additive capable of forming a stable structure represented by the following formula (I) is not added with respect to Examples 1 to 12. TIFF2025096178000039.tif7170

[0057] [Comparative Example 9] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (AMANDARRY, A107S), and PAN are mixed at a weight ratio of 3.2:4:92:0.8, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0058] In Comparative Example 9, no additive capable of forming a stable structure represented by the following formula (I) is added to Examples 1 to 12. TIFF2025096178000040.tif7170

[0059] [Comparative Example 10] PAN, commercial carbon powder (Super P), and commercial sodium cathode material (AMANDARRY, A107S) are mixed at a weight ratio of 4:4:92, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0060] In Comparative Example 10, no additive capable of forming a stable structure represented by the following formula (I) is added to Examples 1 to 12. TIFF2025096178000041.tif7170

[0061] [Comparative Example 11] Commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), and commercial sodium cathode material (AMANDARRY, A107S) are mixed at a weight ratio of 4:4:92, and stirred for 30 minutes by a rotary degassing machine (Hongyi Co., Ltd.) using NMP as a solvent. The mixed slurry is allowed to stand, and the change in its viscosity over time is observed.

[0062] In Comparative Example 11, no additive capable of forming a stable structure represented by the following formula (I) is added to Examples 1 to 12. TIFF2025096178000042.tif7170

[0063] [Test Example] Measure the change over time in the viscosity of the slurries in the above-described Examples 1 to 12 and Comparative Examples 1 to 11, and the presence or absence of a gelation phenomenon. The measurement results are shown in Table 1 below.

[0064] [Table 1]

[0065] In Table 1, the unit of viscosity is cps, and Gel indicates that the gelation phenomenon was observed and thus the viscosity could not be measured.

[0066] As shown in Table 1 above, compared with Comparative Examples 1 to 11, Examples 1 to 12 show better viscosity characteristics of the produced electrode slurries by containing specific compounds or polymers.

[0067] In addition, the compounds or polymers contained in Examples 1 to 12 can form a stable structure represented by the following formula (I), and X is By resonating with TIFF2025096178000044.tif6170, the structure of formula (I) is stabilized. Thereby, an electrode slurry showing better viscosity characteristics can be produced. On the other hand, since the compounds or polymers contained in Comparative Examples 1 to 11 cannot form the above structure, the electrode slurries produced in Comparative Examples 1 to 11 show poor viscosity characteristics. TIFF2025096178000045.tif7170

[0068] The present invention is not limited to the above-described respective examples, and various modifications are possible within the scope shown in the claims. Examples obtained by appropriately combining the technical means disclosed in different examples are also included in the technical scope of the present invention.

Claims

1. The composition comprises one or more compounds or polymers that form a stable structure according to formula (I), The X is By resonating with, the structure of formula (I) is stabilized. Electrode slurries used in electrochemical energy storage devices.

2. The X is The organic moiety is selected from The R 1 and the R 2 is a substituent selected from the group consisting of linear or cyclic alkyl groups, aryl groups and derivatives thereof, R is a substituent selected from the group consisting of an alkyl group, a carboxyl group, a carbonyl group, a hydroxyl group and derivatives thereof; The electrode slurry of claim 1.

3. Further comprising lithium, sodium or compounds thereof; The electrode slurry of claim 1.

4. Further comprising a polymer or copolymer derived from vinylidene fluoride (VDF) and / or acrylonitrile (AN) monomers; The electrode slurry of claim 1.

5. The copolymer has the following structure: G I is derived from acrylonitrile, G II is derived from an acrylate or methacrylate, and said R 4 is a straight chain alkyl group, G III is derived from a vinyl lactam compound, and A is a cyclic amide group, G IV is derived from acrylic acid or methacrylic acid, The R 3 is H or CH 3 and The number of constituent repeating units of the copolymer satisfies the following formula: The electrode slurry of claim 4.

6. In the copolymer, the G I is 50 to 98% by weight, II is 0.5 to 20% by weight, III is 0.5 to 20% by weight, IV is 0.5 to 20% by weight, The electrode slurry of claim 5.

7. The compound or polymer is 0.001 to 10% by weight based on the total solid content of the electrode slurry; The electrode slurry of claim 1.

8. The compound or polymer is selected from the group consisting of compounds containing a phenolic moiety, compounds containing an aminoxide moiety, phenols, and derivatives or derived polymers thereof; The electrode slurry of claim 1.

9. The compound or polymer is selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine oxide, tetramethylpiperidine oxide, phenol, polyphenol, hydroquinone, hydroquinone monomethyl ether, and derivatives or derived polymers thereof; The electrode slurry of claim 8.

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