Electrode pastes for electrochemical energy storage devices

Abstract

An electrode paste for an electrochemical energy storage device comprises one or more compounds or polymers that can form a stable structure represented by the following column Formula (I): # imgabs0 # imgabs1 # and wherein X can resonate with # imgabs2 # to stabilize the structure of Formula (I).

Description

Technical Field

[0001] The present invention relates to an electrode paste for an electrochemical energy storage device, and particularly to an electrode paste for an electrochemical energy storage device, which comprises one or more compounds or polymers that can form a stable structure represented by the following formula (I): and wherein X can resonate with to stabilize the structure of formula (I). Background Art

[0002] Electrochemical energy storage devices are widely used in various electronic products. The physical and chemical properties of the electrode paste used in an electrochemical energy storage device have a certain impact on the charge-discharge efficiency of the electrochemical energy storage device. Among them, the viscosity of the electrode paste and the trend of the viscosity of the electrode paste changing with time have a significant impact on the manufacturing difficulty of the electrochemical energy storage device, as well as the yield and lifespan of the product.

[0003] The prior art has attempted to add compounds or polymers to the electrode paste for an electrochemical energy storage device to improve its viscosity properties. However, there is still room for improvement in the control of viscosity in the electrode paste for an electrochemical energy storage device in the prior art. Summary of the Invention

[0004] There is still room for improvement in the control of viscosity in the electrode paste for an electrochemical energy storage device in the prior art. Therefore, an object of the present invention is to provide a novel electrode paste for an electrochemical energy storage device, which can effectively control the residual alkali of the positive electrode active material and its side reactions, and has good viscosity properties.

[0005] To achieve the above object and other objects, the present invention provides an electrode paste for an electrochemical energy storage device, comprising:

[0006] One or more compounds or polymers that can form a stable structure represented by the following formula (I):

[0007]

[0008] and wherein X can resonate with to stabilize the structure of formula (I).

[0009] In the above electrode paste, the X moiety can be an organic moiety selected from wherein R1 and R2 are substituents selected from the group consisting of linear or cyclic alkyl groups, aryl groups, and their derivatives.

[0010] wherein, R1 and R2 are substituents selected from the group consisting of linear or cyclic alkyl groups, aryl groups, and their derivatives.

[0011] Among them, R is a substituent selected from the group consisting of alkyl, carboxyl, carbonyl, hydroxyl and their derivatives.

[0012] The above electrode paste may further include: lithium, sodium or their compounds.

[0013] The above electrode paste may further include: a polymer or copolymer containing monomers derived from vinylidene fluoride (VDF) and / or acrylonitrile (AN).

[0014] The above electrode paste, wherein the copolymer may have a structure as shown below:

[0015]

[0016] Wherein:

[0017] G I Derived from acrylonitrile;

[0018] G II Derived from acrylate or methacrylate, and R4 is a straight-chain alkyl group;

[0019] G III Derived from an ethylene lactam compound, and A is a cyclic amide group;

[0020] G IV Derived from acrylic acid;

[0021] Wherein R3 is H or CH3;

[0022] Among them, the number of repeating units of the copolymer meets the following conditions:

[0023]

[0024] The above electrode paste, wherein G I May account for 50-98 wt% of the copolymer, G II May account for 0.5-20 wt% of the copolymer, G III May account for 0.5-20 wt% of the copolymer, G IV May account for 0.5-20 wt% of the copolymer; wherein G III May be derived from vinylpyrrolidone.

[0025] The above electrode paste, wherein the compound or polymer may account for 0.001-10 wt% of the solid weight of the electrode paste.

[0026] The above-mentioned electrode paste, wherein the compound containing oxygen, nitrogen or sulfur can be freely selected from compounds having the following types of functional groups, but is not limited to the following compounds, such as aldehydes: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, glucose, benzaldehyde; piperidine or pyrrolidine compounds: pyrrolidine, pyrroline, pyrrole, hexahydropiperidine, tetramethylpiperidine oxide, N-methylpiperidine-2-ethanol, R-3-aminopiperidine hydrochloride; phenols: phenol, polyphenol, hydroquinone, bisphenol A, dibutylhydroxytoluene, 2-methylphenol, 2-isopropyl-5-methylphenol, hindered phenol, xylenol, monomethyl ether of hydroquinone, propofol, nonylphenol, cresol, salicylic acid, methyl salicylate, phenolic resin and its derivatives; nitriles: acetonitrile, acetonitrile, hydrogen cyanide, cyanic acid, cyanuric acid, thiocyanic acid, malononitrile, succinonitrile, acrylonitrile, vitamin B12, potassium ferrocyanide, potassium nickel cyanide, potassium cobalt cyanide, Prussian blue, potassium silver cyanide, potassium gold cyanide, potassium cyanide, sodium cyanide, zinc cyanide, silver cyanide, cuprous cyanide, mercuric cyanide, nickel cyanide, cobalt cyanide, polyacrylonitrile and ketones: aliphatic ketones, alicyclic ketones and aromatic ketones, acetone, butanone, methyl ethyl ketone, cyclohexanone, butanedione, acetylacetone.

[0027] The above-mentioned electrode paste, wherein the compound or polymer is preferably selected from the group consisting of compounds containing a phenolic moiety, compounds containing an aminoxide moiety, phenols and their derivatives or their derived polymers.

[0028] The above-mentioned electrode paste, wherein the compound or polymer is preferably selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy, tetramethylpiperidine oxide, phenol, polyphenol, hydroquinone and monomethyl ether of hydroquinone and their derivatives or their derived polymers.

[0029] Compared with the prior art, the electrode paste for an electrochemical energy storage device of the present invention has preferable viscosity properties. Detailed Description of the Invention

[0030] To fully understand the purpose, features and effects of the present invention, the present invention will be described in detail by the following specific examples as follows:

[0031] Example 1

[0032] Using polyacrylonitrile copolymer as an anti-gel additive, it is mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and phenol additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:10, and N-methyl-2-pyrrolidone (NMP) is used as a solvent, and stirred with a rotary degassing machine (Hongyi) for 30 minutes. The stirred slurry is left standing and the change in viscosity over time is observed.

[0033] Among them, the phenol additive can form a stable structure as shown in the following formula (I):

[0034]

[0035] And X can resonate with to stabilize the structure of formula (I).

[0036] Example 2

[0037] Using polyacrylonitrile copolymer as an anti-gel additive, it is mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and phenol additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:20, and NMP is used as a solvent, and stirred with a rotary degassing machine (Hongyi) for 30 minutes. The stirred slurry is left standing and the change in viscosity over time is observed.

[0038] Among them, the phenol additive can form a stable structure as shown in the following formula (I):

[0039]

[0040] And X can resonate with to stabilize the structure of formula (I).

[0041] Example 3

[0042] Using polyacrylonitrile copolymer as an anti-gel additive, it is mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and piperidine additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:10, and NMP is used as a solvent, and stirred with a rotary degassing machine (Hongyi) for 30 minutes. The stirred slurry is left standing and the change in viscosity over time is observed.

[0043] Among them, the piperidine additive can form a stable structure as shown in the following formula (I):

[0044]

[0045] and wherein X can resonate with to stabilize the structure of formula (I).

[0046] Example 4

[0047] Using polyacrylonitrile copolymer as an anti-gel additive, it is mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and piperidine additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:20, and NMP is used as a solvent, and stirred with a rotary degassing machine (Hongyi) for 30 minutes. The stirred slurry is allowed to stand and the change in viscosity over time is observed.

[0048] Among them, the piperidine additive can form a stable structure as shown in the following formula (I):

[0049]

[0050] and wherein X can resonate with to stabilize the structure of formula (I).

[0051] Example 5

[0052] Using polyacrylonitrile copolymer as an anti-gel additive, it is mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and hindered phenol additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:10, and NMP is used as a solvent, and stirred with a rotary degassing machine (Hongyi) for 30 minutes. The stirred slurry is allowed to stand and the change in viscosity over time is observed.

[0053] Among them, the hindered phenol additive can form a stable structure as shown in the following formula (I):

[0054]

[0055] and wherein X can resonate with to stabilize the structure of formula (I).

[0056] Example 6

[0057] Using polyacrylonitrile copolymer as an anti-gel additive, it is mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a hindered phenol additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:20, and NMP is used as a solvent, and it is stirred for 30 minutes with a rotary degassing machine (Hongyi). The stirred slurry is allowed to stand and the change in viscosity over time is observed.

[0058] Among them, the hindered phenol additive can form a stable structure as shown in the following formula (I):

[0059]

[0060] And where X can resonate with to stabilize the structure of formula (I).

[0061] Example 7

[0062] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a piperidine additive in a weight ratio of 3.6:4:92:0.4, use NMP as a solvent, and stir for 30 minutes with a rotary degassing machine (Hongyi). The stirred slurry is allowed to stand and the change in viscosity over time is observed.

[0063] Among them, the piperidine additive can form a stable structure as shown in the following formula (I):

[0064]

[0065] And where X can resonate with to stabilize the structure of formula (I).

[0066] Example 8

[0067] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a hindered phenol additive in a weight ratio of 3.6:4:92:0.4, use NMP as a solvent, and stir for 30 minutes with a rotary degassing machine (Hongyi). The stirred slurry is allowed to stand and the change in viscosity over time is observed.

[0068] Among them, the hindered phenol additive can form a stable structure as shown in the following formula (I):

[0069]

[0070] And where X can resonate with to stabilize the structure of formula (I).

[0071] Example 9

[0072] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a piperidine additive in a weight ratio of 3.2:4:92:0.8, and use NMP as a solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0073] Among them, the piperidine additive can form a stable structure as shown in the following formula (I):

[0074]

[0075] And X can resonate with to stabilize the structure of formula (I).

[0076] Example 10

[0077] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a hindered phenol additive in a weight ratio of 3.2:4:92:0.8, and use NMP as a solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0078] Among them, the hindered phenol additive can form a stable structure as shown in the following formula (I):

[0079]

[0080] And X can resonate with to stabilize the structure of formula (I).

[0081] Example 11

[0082] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a hydroquinone additive in a weight ratio of 3.6:4:92:0.4, and use NMP as a solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0083] Among them, the hydroquinone additive can form a stable structure as shown in the following formula (I):

[0084]

[0085] And X can resonate with to stabilize the structure of formula (I).

[0086] Example 12

[0087] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a hydroquinone additive in a weight ratio of 3.2:4:92:0.8, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0088] Among them, the hydroquinone additive can form a stable structure as shown in the following formula (I):

[0089]

[0090] And X can resonate with to stabilize the structure of formula (I).

[0091] Comparative Example 1

[0092] Mix a polyacrylonitrile copolymer as an anti-gel additive, a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and an aldehyde additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:10, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0093] Compared with Examples 1 to 12, the aldehyde additive used in Comparative Example 1 cannot form a stable structure as shown in the following formula (I):

[0094]

[0095] Comparative Example 2

[0096] Mix a polyacrylonitrile copolymer as an anti-gel additive, a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and an aldehyde additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:20, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0097] Compared with Examples 1 to 12, the aldehyde additive used in Comparative Example 2 cannot form a stable structure as shown in the following formula (I):

[0098]

[0099] Comparative Example 3

[0100] Polyacrylonitrile copolymer was used as an anti-gel additive and mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a ketone additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:10. NMP was used as the solvent, and a rotary degassing machine (Hongyi) was used to stir for 30 minutes. The stirred slurry was allowed to stand, and the change in viscosity over time was observed.

[0101] Compared with Examples 1 to 12, the ketone additive used in Comparative Example 3 could not form a stable structure as shown in the following formula (I):

[0102]

[0103] Comparative Example 4

[0104] Polyacrylonitrile copolymer was used as an anti-gel additive and mixed with a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and a ketone additive as an adjuvant in a weight ratio of 0.8:3.2:4:92:80. NMP was used as the solvent, and a rotary degassing machine (Hongyi) was used to stir for 30 minutes. The stirred slurry was allowed to stand, and the change in viscosity over time was observed.

[0105] Compared with Examples 1 to 12, the ketone additive used in Comparative Example 4 could not form a stable structure as shown in the following formula (I):

[0106]

[0107] Comparative Example 5

[0108] Polyacrylonitrile copolymer was used as an adhesive and mixed with commercial carbon powder (Super P) and commercial sodium cathode material (Medary, A107S) in a weight ratio of 4:4:92. NMP was used as the solvent, and a rotary degassing machine (Hongyi) was used to stir for 30 minutes. The stirred slurry was allowed to stand, and the change in viscosity over time was observed.

[0109] Compared with Examples 1 to 12, Comparative Example 5 did not add an additive that could form a stable structure as shown in the following formula (I):

[0110]

[0111] Comparative Example 6

[0112] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and an aldehyde additive in a weight ratio of 3.6:4:92:0.4, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0113] Compared with Examples 1 to 12, the aldehyde additive used in Comparative Example 6 cannot form a stable structure as shown in the following formula (I):

[0114]

[0115] Comparative Example 7

[0116] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and an aldehyde additive in a weight ratio of 3.2:4:92:0.8, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0117] Compared with Examples 1 to 12, the aldehyde additive used in Comparative Example 7 cannot form a stable structure as shown in the following formula (I):

[0118]

[0119] Comparative Example 8

[0120] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and polyacrylonitrile (Polyacrylonitrile, PAN) in a weight ratio of 3.6:4:92:0.4, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0121] Compared with Examples 1 to 12, Comparative Example 8 did not add an additive that can form a stable structure as shown in the following formula (I):

[0122]

[0123] Comparative Example 9

[0124] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), commercial sodium cathode material (Medary, A107S), and PAN in a weight ratio of 3.2:4:92:0.8, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0125] Compared with Examples 1 to 12, Comparative Example 9 did not add an additive that can form a stable structure shown in the following formula (I):

[0126]

[0127] Comparative Example 10

[0128] Mix PAN, commercial carbon powder (Super P), and commercial sodium cathode material (Medary, A107S) in a weight ratio of 4:4:92, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0129] Compared with Examples 1 to 12, Comparative Example 10 did not add an additive that can form a stable structure shown in the following formula (I):

[0130]

[0131] Comparative Example 11

[0132] Mix a commercial adhesive (Solvay, 5130), commercial carbon powder (Super P), and commercial sodium cathode material (Medary, A107S) in a weight ratio of 4:4:92, and use NMP as the solvent. Stir with a rotary degassing machine (Hongyi) for 30 minutes. Let the stirred slurry stand and observe the change in viscosity over time.

[0133] Compared with Examples 1 to 12, Comparative Example 11 did not add an additive that can form a stable structure shown in the following formula (I):

[0134]

[0135] Test Example

[0136] Measure the change in viscosity over time of the slurries of Examples 1 to 22 and Comparative Examples 1 to 11 above, and whether gelation occurs. The measurement results are shown in Table 1 below.

[0137] Table 1

[0138] 0 hours 2 hours 6 hours 9 hours 12 hours 24 hours 48 hours Example 1 3860 4781 10680 Gel Example 2 13238 35878 Gel Example 3 103 198 76 Gel Example 4 234 267.9 186 329.3 3237 Example 5 1994 - - 1064 - Example 6 865 - - 694.5 - Example 7 1321 368 486 Gel Example 8 12100 12912 Gel Example 9 1395 410 396 Gel Example 10 2856 763 1736 57490 Gel Example 11 2093 3181 1327 19440 Gel Example 12 3191 3680 1293 1473 2130 Comparative Example 1 169 171.3 Gel - - Comparative Example 2 90510 Gel Comparative Example 3 1470 930 Gel Comparative Example 4 223 521 Gel Comparative Example 5 78.14 225.1 420 18000 Gel Comparative Example 6 21320 Gel Comparative Example 7 16732 36740 Gel Comparative Example 8 2136 7162 Gel Comparative Example 9 3721 8558 Gel Comparative Example 10 11330 15220 Gel Comparative Example 11 Gel - - - -

[0139] The viscosity unit in Table 1 is cps. Gel indicates that gelation has been observed, so the viscosity cannot be measured.

[0140] As shown in Table 1 above, compared with Comparative Examples 1 to 11, Examples 1 to 12, by including specific compounds or polymers, the electrode slurries prepared therefrom have preferable viscosity properties. Among them, the compounds or polymers included in Examples 1 to 12 can form a stable structure as shown in the following formula (I): And wherein X can resonate with to stabilize the structure of formula (I), thereby enabling the electrode slurries prepared therefrom to have preferable viscosity properties. In contrast, the compounds or polymers included in Comparative Examples 1 to 11 cannot form the above structure, resulting in the electrode slurries prepared therefrom having poor viscosity properties.

[0141] The present invention has been disclosed above with preferred embodiments. However, those skilled in the art should understand that the embodiments are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all equivalent changes and substitutions to the embodiments should be considered as falling within the scope of the present invention. Therefore, the protection scope of the present invention shall be defined by the claims.

Claims

1. An electrode slurry for an electrochemical energy storage device, characterized in that: include: One or more compounds or polymers, which can form a stable structure as shown in the following formula (I): And X can be Resonance stabilizes the structure of formula (I).

2. The electrode slurry according to claim 1, characterized in that: Wherein the X part is selected from The organic part wherein R1 and R2 are substituents selected from the group consisting of linear or cyclic alkyl groups, aryl groups and their derivatives, Wherein, R is a substituent selected from the group consisting of alkyl, carboxyl, carbonyl, hydroxyl and derivatives thereof.

3. The electrode slurry according to claim 1, characterized in that: Further including: Lithium, sodium or their compounds.

4. The electrode slurry according to claim 1, characterized in that: Further including: Contains polymers or copolymers derived from vinylidene fluoride and / or acrylonitrile monomers.

5. The electrode slurry according to claim 4, characterized in that: The copolymer has the following structure: in: G I Derived from acrylonitrile; G II Derived from acrylate or methacrylate, R4 is a linear alkyl group; G III Derived from vinyl lactam compounds, A is a cyclic amide group; G IV Derived from acrylic acid or methacrylic acid; wherein R3 is H or CH3; Wherein, the number of repeating units of the copolymer polymer meets the following conditions:

6. The electrode slurry according to claim 5, characterized in that: Among them G I Accounting for 50-98wt% of the copolymer polymer, G II Accounting for 0.5-20wt% of the copolymer polymer, G III Accounting for 0.5-20wt% of the copolymer polymer, G IV It accounts for 0.5 to 20 wt% of the copolymer.

7. The electrode slurry according to claim 1, characterized in that: The compound or polymer accounts for 0.001 to 10 wt % of the solid weight of the electrode slurry.

8. The electrode slurry according to claim 1, characterized in that: The compound or polymer is selected from the group consisting of compounds containing phenolic moieties, compounds containing amino oxide moieties, phenols and their derivatives or derived polymers thereof.

9. The electrode slurry according to claim 8, characterized in that: The compound or polymer is selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinium oxide, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinium oxide, tetramethylpiperidinium oxide, phenol, polyphenols, hydroquinone and hydroquinone monomethyl ether and their derivatives or derived polymers.

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