CN102130338A - Lithium-ion battery water-based cathode slurry and preparation method thereof - Google Patents
Lithium-ion battery water-based cathode slurry and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of preparation of lithium ion battery slurry, and discloses lithium ion battery water-based anode slurry which comprises 40-80 parts by weight of active substances, 25-50 parts by weight of solvents, 1-5 parts by weight of surfactants, 1-3 parts by weight of thickeners, 2-6 parts by weight of conductive agents and 2-4 parts by weight of adhesives, wherein the solvents are one or two of deionized water and isopropanol, the surfactants are anionic surfactants, the thickeners are one or two of sodium carboxymethylcellulose and polyacrylamide, and the adhesives are one or more of styrene-butadiene latex, polyvinyl alcohol and polyacrylate. Compared with the prior art, the invention does not use organic solvent which pollutes the environment and is difficult to recover, is environment-friendly, and the boiling point of a water-based system is lower, so the preparation process saves more energy, reduces the cost and simultaneously can improve the production efficiency.
Description
Technical field
The present invention relates to a kind of lithium ion battery anode glue size, relate in particular to a kind of environmentally friendly water base anode sizing agent and preparation method thereof.
Background technology
In the lithium ion battery preparation process, active material need be prepared into homodisperse slurry, be coated on the collector then.For positive electrode, usually adopt one or more making slurries in organic solvent such as N-methyl pyrrolidone, dimethyl formamide, cyclohexanone, diethylformamide, the dimethyl sulfoxide (DMSO), adopt these solvents mainly to be because it can dissolve bonding agent PVDF.But the boiling point of above-mentioned solvent is higher, needs more heat energy in the evaporation drying course, and can cause serious pollution to environment after evaporateing in the air.If recycle then need to consume a large amount of energy, and can't realize that 100% of solvent reclaims.Therefore, provide a kind of energy savings and can not cause the anode sizing agent system of environmental pollution to become particularly important.
In order to address the above problem, industry begins to attempt adopting aqueous based systems to prepare anode sizing agent, but the result is very undesirable, is difficult to reach commercial requirement of using.
Summary of the invention
The objective of the invention is to: a kind of energy savings is provided and is beneficial to the water base anode sizing agent of lithium ion battery of environmental protection, and the preparation method of slurry is provided.
To achieve these goals, the inventor is through concentrating on studies, find that the restriction anode sizing agent adopts aqueous based systems preparation technology's reason to mainly contain two: the first, the stability problem of positive electrode itself, though cobalt acid lithium is the constitutionally stable positive electrode of generally acknowledging, materials such as lithium titanate are because the unsteadiness of this body structure causes it can not adopt the water-based slurry preparation; The second, the stability problem of auxiliary material itself, because the operating voltage of lithium ion battery is generally 3.0-4.2V, and auxiliary material, for example, thickener, surfactant and bonding agent etc. still can remain in after cell preparation is finished in the pole piece, and in the lithium ion battery charging and discharging process, the auxiliary material in the positive plate tend to take place oxidation decomposition under lower recovery voltage, even so that more stable active material such as cobalt acid lithium, can not select the unsettled auxiliary material of performance.
Through experiment and screening repeatedly, the present invention has found the water-based solvent and the auxiliary material that can be applicable to unstable positive electrode, and provide a kind of water base anode sizing agent in view of the above, it comprises: the active material of 40～80 weight portions, the solvent of 25～50 weight portions, the surfactant of 1～5 weight portion, the thickener of 1～3 weight portion, the conductive agent of 2～6 weight portions, the bonding agent of 2～4 weight portions, solvent is a deionized water, in the isopropyl alcohol one or both, surfactant is an anionic surfactant, thickener is a sodium carboxymethylcellulose, in the polyacrylamide one or both, bonding agent are styrene-butadiene latex, polyvinyl alcohol, in the polyacrylate one or more.
Described positive active material comprises one or more in cobalt acid lithium, LiMn2O4, LiFePO4, lithium manganese phosphate, the lithium nickel cobalt manganese.
The ratio that described isopropyl alcohol accounts for the solvent total weight is not more than 40%.
Described anionic surfactant comprises one or more in dispersant, wetting agent, defoamer, levelling agent, the pH value conditioning agent.
Described dispersant is one or more in polyoxyethylene ether block copolymers, polyamine salt, the alcohols, is polyoxyethylene ether block copolymers between 2000～5000 as number-average molecular weight.
Described wetting agent is a polyethenoxy alkylphenols, and its number-average molecular weight is between 5000～8000.
Described defoamer is polysiloxanes and modifier thereof, as 8034,8034A, A10.
Described levelling agent is one or more in polysilanes (being silicone oil), ester class, the alcohols, is the mixture of 1:1 as silicone oil and vinyl acetate ratio.
Described pH value conditioning agent is an organic amine, as 2-amino-2-methyl-1-propanol.
Described conductive agent is a conductive carbon.
The solids content of described anode sizing agent is 40%～75%, viscosity 3000～8000mpas.
In order to solve the problems of the technologies described above, the present invention also provides the preparation method of the water base anode sizing agent of a kind of lithium ion battery, it is characterized in that, may further comprise the steps: load weighted solvent is added in the container, in solvent, add surfactant, thickener, add conductive agent, active material after being uniformly dispersed successively, add binding agent again, finally make water base anode sizing agent.
Surfactant in the described direct adding solvent is dispersant and defoamer.
Can also continue to add the pH value conditioning agent after adding binding agent.
With respect to prior art, the organic solvent that the present invention does not re-use contaminated environment and is difficult to reclaim, environmentally friendly, and the boiling point of aqueous based systems is lower, so preparation process energy savings more, reduce cost; Owing to adopted the surfactant of multiple functional and stable electrochemical property, it interacts and has effectively improved body series stability of slurry and processing characteristics, improved production efficiency greatly, itself all has more stable chemical property bonding agent of the present invention, helps the lifting of battery performance.
Description of drawings
Below in conjunction with the drawings and specific embodiments, the present invention and useful technique effect thereof are elaborated.
Fig. 1 is the electromicroscopic photograph of the pole piece made of each embodiment and Comparative Examples anode sizing agent.
Fig. 2 is the time dependent curve of viscosity of each embodiment and Comparative Examples anode sizing agent.
Fig. 3 is the change curve at the phase angle of each embodiment and Comparative Examples anode sizing agent.
Embodiment
The non-active ingredients such as surfactant, thickener and bonding agent that use in the water base anode sizing agent of lithium ion battery of the present invention, it all is the indispensable composition of selecting through meticulously of the water base anode sizing agent of preparation, they all have stable chemical property, and its interaction energy is effectively improved body series stability of slurry and processing characteristics, therefore can be applicable to unstable positive electrode, the main effect in slurry is dispersive property, increase stability of slurry energy and a processing characteristics of improving slurry.
Below will describe the main component and the preparation process of the water base anode sizing agent of lithium ion battery of the present invention in detail by embodiment.
Embodiment 1
Weighing 200kg deionized water joins in the container, the polyacrylamide thickener that slowly adds 4Kg dispersant (number-average molecular weight is 3000 polyoxyethylene ether block copolymers), 1.2KG defoamer polysiloxanes (marque is A10), 5Kg sodium carboxymethyl cellulose thickener, 5kg then, add 9Kg conductive carbon (Super " p " Li), 300Kg active material cobalt acid lithium after being uniformly dispersed again successively, add 10Kg bonding agent styrene-butadiene latex again, finally be prepared into the water base anode sizing agent of solids content 60%～70%, viscosity 3000～8000mpas.
Embodiment 2
Weighing 200kg deionized water, the 20Kg isopropyl alcohol joins in the container, the dispersant that slowly adds 5Kg polyoxyethylene ether block copolymers then, (its number-average molecular weight is 6000 to 1Kg wetting agent polyethenoxy alkylphenols, as marque PE100), 1Kg defoamer polysiloxanes (marque is 8034), the 5Kg sodium carboxymethyl cellulose thickener, add 12Kg conductive carbon (Super " p " Li) after being uniformly dispersed again successively, 300Kg active material LiMn2O4, add 12Kg bonding agent polyvinyl alcohol again, finally be prepared into solids content 60%～70%, the water base anode sizing agent of viscosity 3000～6000mpas.
Embodiment 3
Weighing 60kg deionized water, the 40Kg isopropyl alcohol joins in the container, the dispersant (as marque AFX1080) that slowly adds 8Kg polyoxyethylene ether block copolymers then, adding 2Kg silicone oil and vinyl acetate ratio is the levelling agent of the mixture of 1:1,2Kg defoamer polysiloxanes (marque is 8034A), the 10Kg sodium carboxymethyl cellulose thickener, 2kg polyacrylamide thickener, add 15Kg conductive carbon (Super " p " Li) after being uniformly dispersed again successively, the 200Kg active compound lithium iron phosphate, add 8Kg bonding agent polyacrylate again, add 0.3Kg pH value conditioning agent 2-amino-2-methyl-1-propanol (as marque Conspirit 950) again, finally be prepared into solids content 65%～75%, the water base anode sizing agent of viscosity 3000～6000mpas.
Embodiment 4
Weighing 190kg deionized water, the 50Kg isopropyl alcohol joins in the container, the dispersant (as marque AFX1080) that slowly adds 5Kg polyoxyethylene ether block copolymers then, 1Kg defoamer polysiloxanes (marque is 8034A), the 12Kg sodium carboxymethyl cellulose thickener, add 12Kg conductive carbon (Super " p " Li) after being uniformly dispersed again successively, 280Kg active material lithium manganese phosphate, add the 24Kg styrene-butadiene latex again, add 0.4Kg pH value conditioning agent 2-amino-2-methyl-1-propanol (as marque AMP-95) again, finally be prepared into solids content 50%～70%, the water base anode sizing agent of viscosity 3000～5000mpas.
Embodiment 5
Weighing 200kg deionized water, the 100Kg isopropyl alcohol joins in the container, the dispersant (as marque PE100) that slowly adds 15Kg polyoxyethylene ether block copolymers then, 3Kg defoamer polysiloxanes (marque is A10), the 10Kg sodium carboxymethyl cellulose thickener, add 12Kg conductive carbon (Super " p " Li) after being uniformly dispersed again successively, 350Kg active material lithium-nickel-cobalt manganese ternary material, add 10Kg polyacrylate bonding agent again, add 1Kg pH value conditioning agent 2-amino-2-methyl-1-propanol (as marque AMP-95) again, finally be prepared into solids content 40%～50%, the water base anode sizing agent of viscosity 3000～6000mpas.
For the various performances of the water base anode sizing agent of the present invention are described, now preparing five parts of oil that are used to contrast of Comparative Examples 1-5 is anode sizing agent.
Comparative Examples 1
Weighing 200kgN-methyl pyrrolidone joins in the container, slowly add 6kg Kynoar stirring and dissolving then, add 6Kg carbonaceous conductive agent Super " p " Li, 120kg cobalt acid lithium more successively, finally be prepared into the oil base anode sizing agent of solids content 60%～75%, viscosity 3000～10000mpas.
Comparative Examples 2
Weighing 200kgN-methyl pyrrolidone joins in the container, slowly add 12kg Kynoar stirring and dissolving then, add 6Kg carbonaceous conductive agent Super " p " Li, 300Kg active material LiMn2O4 more successively, finally be prepared into the oil base anode sizing agent of solids content 60%～70%, viscosity 3000～10000mpas.
Comparative Examples 3
Weighing 200kgN-methyl pyrrolidone joins in the container, slowly add 20kg Kynoar stirring and dissolving then, add 6Kg carbonaceous conductive agent Super " p " Li, 120Kg active compound lithium iron phosphate more successively, finally be prepared into the oil base anode sizing agent of solids content 30%～70%, viscosity 5000～10000mpas.
Comparative Examples 4
Weighing 200kgN-methyl pyrrolidone joins in the container, slowly add 20kg Kynoar stirring and dissolving then, add 6Kg carbonaceous conductive agent Super " p " Li, 300kg active material lithium manganese phosphate etc. more successively, finally be prepared into the oil base anode sizing agent of solids content 50%～70%, viscosity 5000～10000mpas.
Comparative Examples 5
Weighing 200kgN-methyl pyrrolidone joins in the container, slowly add 12kg Kynoar stirring and dissolving then, add 8Kg carbonaceous conductive agent Super " p " Li, 300Kg active material lithium-nickel-cobalt manganese etc. more successively, finally be prepared into the oil base anode sizing agent of solids content 60%～70%, viscosity 5000～10000mpas.
Anode sizing agent in the preparation of the foregoing description and Comparative Examples is coated with on coating machine by the Model (as 383450,053448,18650) of design makes anode pole piece, and the anode pole piece of making cut and is assembled into electric core, perfusion electrolyte carries out chemical membrane, aging, by Performance Detection, the stability and the beneficial effect of the water base anode sizing agent of the present invention is described to anode pole piece and electric core.Detect the chemical property of electric core, scan electric core with EIS and CV and carry out performance evaluation.
Performance evaluation 1---dispersion effect evaluation: the surface and the section of the anode pole piece of the anode sizing agent that utilizes embodiment and Comparative Examples being made with ESEM (SEM) carry out analyzing and testing, the result as shown in Figure 1, Electronic Speculum picture from figure as can be known, in the pole piece that the water base anode sizing agent of the present invention makes, the dispersive property of powder is compared almost with the oil base anode sizing agent, conductive carbon material is reunited, and illustrates that dispersive property of the present invention can accept.
Performance evaluation 2---slurry estimation of stability: the viscosity of anode sizing agent is in 3000～10000mpas the time, slurry can not precipitate usually, cause that the unsettled principal element of slurry is that the viscosity of slurry can rise with the prolongation of resting period, and then cause the slurry coating performance not good enough.For this reason, investigated the time dependent curve of slurry viscosity in embodiment and the Comparative Examples, the result as shown in Figure 2.As seen, the trend that the slurry viscosity of oil based system rises with the prolongation of resting period is very obvious, but the viscosity of water-based slurry of the present invention then can keep stable state in long-time, the weight of pole piece just can not fluctuate on a large scale in the process of coating like this, not only be suitable for the high speed transfer coating, and the consistency of the capacity of the electric core of preparation and other performances is very good, has effectively reduced the difficulty and the workload of electric core grouping and assembling aspect.
Performance evaluation 3---preparation slurry is with the estimation of stability of auxiliary material: the slurry of each embodiment is filmed on aluminium foil and be prepared into 2032 button cells, add the electrolyte of identical type, be assembled into battery, with 1480 electrochemical workstations circular button half-cell is carried out CV scanning then, button cell model: 2032, scanning voltage: 0-6V, sweep speed: 20uv/s, the result shows: in 0～4.2 volt, the employed auxiliary material of aqueous based systems of the present invention there is no redox reaction and take place, explanation is in the operating voltage range of lithium ion battery, and the stable chemical performance of these auxiliary material side reaction can not take place.
Performance evaluation 4---water-based slurry positive electrode estimation of stability: adopt 2032 button cells, the pulp preparation of each embodiment and Comparative Examples is become pole piece, add the electrolyte of identical type, be assembled into battery, and the capacity of test button cell, the result shows that the button cell capacity of aqueous based systems embodiment is compared with oil based system and is more or less the same, illustrates that aqueous based systems anode sizing agent of the present invention is stable.
Performance evaluation 5---stir and the coating performance evaluation: test the stirring and the coating performance of each embodiment and Comparative Examples, the result is as shown in table 1.
By table 1 as seen, adopt the more original oil based system of mixing time of aqueous based systems to shorten more than 50%, and the slurry solid content of different positive electrodes all has a certain upgrade, because the boiling point of water and isopropyl alcohol is low far beyond organic solvent such as NMP, so the coating speed of water-based slurry and efficient have also obtained bigger lifting, saved a large amount of heat energy simultaneously, the outward appearance of filming also is highly improved.
Simultaneously owing to adopted the surfactant of multiple functional and stable electrochemical property, it interacts and has effectively improved body series stability of slurry and processing characteristics, Fig. 3 adopts the embodiment of rheometer test and the phase angle of Comparative Examples, for existing coating machine (comma roller coat cloth, extrusion coated etc.), slurry need have preferably viscoelasticity can could be realized stablizing and high-speed coating, and the viscoelasticity of slurry can characterize with the phase angle, the phase angle is big more, and the phase angle is better with more little its coating performance of slurry of the variation of shearing frequency.As seen from Figure 3, surfactant by adding appropriate amount and optimize its ratio, more than phase angle height to 60 degree of slurry, and the variation at phase angle is less, the application rate of slurry can reach 8～15m/min in the case, 2～the 5m/min that is higher than Comparative Examples far away can enhance productivity so greatly.
Performance evaluation 6---full battery performance influence is estimated: the electric core that utilizes each embodiment and Comparative Examples slurry to make is changed into, and testing capability retention under the high rate performance, low temperature of electric core and normal temperature, the loop test under 45 ℃ and 60 ℃ respectively by UL 1642 standards, the result who obtains is as shown in table 2.
By table 2 as seen, compare with the oil base slurry, adopt the full anode gram volume of water-based slurry preparation to bring into normal play, capability retention slightly improves under the high rate performance of battery and the low temperature, the life-span of battery then has a distinct increment, the original defective of cycle performance difference at high temperature of materials such as some materials such as embodiment 2, embodiment 3 also obtains improvement in various degree, illustrates and adopts aqueous based systems than oil based system more obvious advantage to be arranged.
Performance evaluation 7---electric core electrical property is estimated: for LiFePO 4 material, because the unsteadiness of positive electrode structure in cyclic process, and inevitably there is unreacted iron compound in the material building-up process, cause some iron ions from positive pole dissolving pass then barrier film arrive negative pole and negative pole be reduced into iron simple substance and crystallization on barrier film, make inside battery produce micro-short circuit, cause lithium ion battery battery drops fast (being similar to ni-mh and lead-acid battery), also can produce more serious potential safety hazard simultaneously.After discovering that the water base LiFePO4 ion battery of the present invention is through long-term the use, on its barrier film the black dotted region can not appear, and the battery of Comparative Examples 3 preparations is through very many black point-like things occurring after circulating for a long time, illustrate and adopt aqueous based systems can effectively suppress the performance degradation of battery in long-term use, can promote the performance of battery, thereby adopt aqueous based systems more to have superiority for LiFePO 4 material etc. than oil based system.
In sum, the present invention has the following advantages: 1) preparation technology is simple, and the pulp preparation time is short; 2) dispersion effect is good; 3) easy to process, especially coating speed is fast, excellent rate height; 4) stable electrochemical property is stable in 0～4.5V voltage; 5) be applicable to cobalt acid lithium, LiMn2O4, LiFePO4, lithium manganese phosphate, lithium nickel cobalt manganese ternary material isoreactivity material, the scope of application is more extensive; 6) improve the chemical property of battery, to battery low temperature, multiplying power, recycle life-span etc. improvement is all arranged.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
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Cited By (14)
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| CN102810662A (en) * | 2012-08-18 | 2012-12-05 | 山东神工海特电子科技有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
| CN103682305A (en) * | 2013-10-15 | 2014-03-26 | 深圳金山电池有限公司 | High-capacity lithium-ion battery anode sizing agent and preparation method thereof |
| CN105431968A (en) * | 2013-08-13 | 2016-03-23 | 大众汽车瓦尔塔微电池研究有限责任两合公司 | Method and composition for producing positive electrodes for lithium ion batteries |
| CN105576285A (en) * | 2015-10-15 | 2016-05-11 | 安徽大学 | Lithium ion battery anode slurry and aqueous polyurethane/polyaniline adhesive thereof |
| CN106531963A (en) * | 2016-09-21 | 2017-03-22 | 珠海光宇电池有限公司 | Negative electrode paste of lithium ion battery and lithium ion battery |
| CN107507956A (en) * | 2017-07-28 | 2017-12-22 | 山东嘉寓润峰新能源有限公司 | Lithium ion battery slurry coating process |
| CN108428865A (en) * | 2018-03-05 | 2018-08-21 | 天臣新能源研究南京有限公司 | A kind of preparation method of lithium ion battery anode slurry |
| CN108511740A (en) * | 2017-03-13 | 2018-09-07 | 万向二三股份公司 | A kind of high-specific-capacity silicon carbon electrode coating preparation method |
| CN109742318A (en) * | 2019-01-07 | 2019-05-10 | 南昌工程学院 | A kind of preparation method of lithium battery cell slurry |
| EP3809489A1 (en) * | 2019-10-14 | 2021-04-21 | ETH Zurich | Aqueous cathode slurry preparation for manufacturing lithium-ion battery cathodes |
| CN113410462A (en) * | 2021-05-27 | 2021-09-17 | 东莞赣锋电子有限公司 | Additive for lithium ion battery positive electrode, positive electrode slurry using same and preparation method thereof |
| CN115084519A (en) * | 2022-06-13 | 2022-09-20 | 蜂巢能源科技(无锡)有限公司 | Lithium iron phosphate system slurry and preparation method and application thereof |
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| WO2025097293A1 (en) | 2023-11-07 | 2025-05-15 | Dow Global Technologies Llc | Cathode compositions containing piperazine derivatives |
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| CN102810662B (en) * | 2012-08-18 | 2014-07-23 | 山东神工海特电子科技有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
| CN102810662A (en) * | 2012-08-18 | 2012-12-05 | 山东神工海特电子科技有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
| CN105431968A (en) * | 2013-08-13 | 2016-03-23 | 大众汽车瓦尔塔微电池研究有限责任两合公司 | Method and composition for producing positive electrodes for lithium ion batteries |
| CN103682305A (en) * | 2013-10-15 | 2014-03-26 | 深圳金山电池有限公司 | High-capacity lithium-ion battery anode sizing agent and preparation method thereof |
| CN103682305B (en) * | 2013-10-15 | 2016-01-20 | 深圳金山电池有限公司 | High capacity lithium ion battery anode sizing agent and preparation method thereof |
| CN105576285B (en) * | 2015-10-15 | 2018-04-03 | 安徽大学 | Lithium ion battery anode slurry and aqueous polyurethane/polyaniline adhesive thereof |
| CN105576285A (en) * | 2015-10-15 | 2016-05-11 | 安徽大学 | Lithium ion battery anode slurry and aqueous polyurethane/polyaniline adhesive thereof |
| CN106531963A (en) * | 2016-09-21 | 2017-03-22 | 珠海光宇电池有限公司 | Negative electrode paste of lithium ion battery and lithium ion battery |
| CN108511740A (en) * | 2017-03-13 | 2018-09-07 | 万向二三股份公司 | A kind of high-specific-capacity silicon carbon electrode coating preparation method |
| CN107507956A (en) * | 2017-07-28 | 2017-12-22 | 山东嘉寓润峰新能源有限公司 | Lithium ion battery slurry coating process |
| CN107507956B (en) * | 2017-07-28 | 2020-02-07 | 山东嘉寓润峰新能源有限公司 | Lithium ion battery slurry coating process |
| CN108428865A (en) * | 2018-03-05 | 2018-08-21 | 天臣新能源研究南京有限公司 | A kind of preparation method of lithium ion battery anode slurry |
| CN109742318A (en) * | 2019-01-07 | 2019-05-10 | 南昌工程学院 | A kind of preparation method of lithium battery cell slurry |
| EP3809489A1 (en) * | 2019-10-14 | 2021-04-21 | ETH Zurich | Aqueous cathode slurry preparation for manufacturing lithium-ion battery cathodes |
| WO2021074237A1 (en) * | 2019-10-14 | 2021-04-22 | Eth Zurich | Aqueous cathode slurry preparation for manufacturing lithium ion battery cathodes |
| CN113410462A (en) * | 2021-05-27 | 2021-09-17 | 东莞赣锋电子有限公司 | Additive for lithium ion battery positive electrode, positive electrode slurry using same and preparation method thereof |
| CN115084519A (en) * | 2022-06-13 | 2022-09-20 | 蜂巢能源科技(无锡)有限公司 | Lithium iron phosphate system slurry and preparation method and application thereof |
| CN115084519B (en) * | 2022-06-13 | 2024-02-09 | 蜂巢能源科技(无锡)有限公司 | Lithium iron phosphate system slurry and preparation method and application thereof |
| CN116344821A (en) * | 2023-04-19 | 2023-06-27 | 湖州南木纳米科技有限公司 | A kind of aqueous cathode slurry and preparation method thereof |
| WO2025097293A1 (en) | 2023-11-07 | 2025-05-15 | Dow Global Technologies Llc | Cathode compositions containing piperazine derivatives |
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Application publication date: 20110720 |