Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/14—Electrodes for lead-acid accumulators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/06—Lead-acid accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/627—Expanders for lead-acid accumulators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to an organic anti-shrinking agent for lead-acid batteries.
• Lead-acid batteries are relatively inexpensive and have stable performance as secondary batteries, so they have been widely used as automobile batteries, portable equipment batteries, computer backup batteries, and communication batteries.
• Patent Document 1 lignin extracted from wood as an organic anti-shrinking agent added to the negative electrode active material
• Lead-acid batteries are required to have various performances. In general, when lignin is added to the negative electrode of lead-acid batteries, effects such as improving discharge performance at low temperatures and suppressing sulfation can be obtained. There is a problem of lower acceptability.
• An object of the present invention is to provide an organic shrinkage agent that further improves the life, capacity, and discharge characteristics while suppressing the deterioration of the charge acceptance of the lead-acid battery described above as much as possible.
• An organic expander for lead-acid batteries characterized by comprising: [2] The organic shrink-proofing agent for lead-acid batteries according to [1], which has a weight-average molecular weight of 18,000 or less. [3] A method for producing the organic pre-scaling agent for lead-acid batteries according to [1], comprising the step of sulfomethylating kraft lignin. [4] A method for producing the organic pre-scaling agent for lead-acid batteries according to [2], comprising the step of sulfomethylating kraft lignin.
• an organic shrinkage agent that further improves the life, capacity, and discharge characteristics while suppressing the deterioration of the charge acceptance of lead-acid batteries as much as possible.
• ⁇ includes end values. That is, "X through Y” includes the values X and Y at both ends.
• the organic anti-shrinking agent for lead-acid batteries of the present invention contains sulfomethylated kraft lignin, and the organic S content contained in this sulfomethylated kraft lignin exceeds 3.8% by mass and is 5.1% by mass. It is below.
• sulfomethylated kraft lignin obtained by introducing sulfonic acid groups into kraft lignin by sulfomethylation is used.
• Kraft lignin is also known as ThioLignin and SulfateLignin.
• kraft lignin a prepared one may be used, or a commercially available product may be used.
• Methods for preparing kraft lignin include an alkaline solution of kraft lignin, a method of spray-drying an alkaline solution of kraft lignin and pulverizing it to obtain powdered kraft lignin, and a method of precipitating an alkaline solution of kraft lignin with an acid to perform acid precipitation. Methods of obtaining kraft lignin are included.
• the alkaline solution of kraft lignin can be obtained by a known method such as that described in JP-A-2000-336589, but is not limited to these methods.
• raw material wood for example, hardwoods, conifers, miscellaneous trees, bamboo, kenaf, bagasse, and empty bunches after palm oil extraction can be used.
• the sulfomethylated kraft lignin used in the present invention has an organic S content of more than 3.8% by mass and not more than 5.1% by mass, more preferably more than 3.8% by mass; It is 8% by mass or less. If the organic S content is too much more than the above upper limit, charge acceptance may be significantly deteriorated, and if the organic S content is too less than the above lower limit, capacity, discharge characteristics, and life may be deteriorated.
• the organic S content contained in the sulfomethylated kraft lignin in the present invention is represented by —SO 3 M (where M represents a hydrogen atom, a monovalent metal salt, or a divalent metal salt) relative to the solid amount of lignin. It means the total amount of sulfur atoms contained in the sulfonic acid (salt) groups and sulfur atoms contained in the kraft lignin skeleton relative to the solid amount of lignin. More specifically, it is a value calculated from the following formula (1).
• Organic S content (mass%) of sulfomethylated kraft lignin Total S content (mass%) - Inorganic S content (mass%) (In formula (1), the S content indicates the S content relative to the amount of lignin solids.)
• the total S content is the total S content contained in the lignin derivatized product and can be quantified by ICP emission spectrometry.
• the inorganic S content can be calculated as the total amount of the SO 3 content, S 2 O 3 content and SO 4 content quantified by ion chromatography.
• the inorganic S content is calculated based on the content of S in the oxide, not on the content of the oxide itself.
• a sulfonic acid (salt) group is generally introduced at the position shown in the following general formula (1) with respect to the C 6 -C 3 unit of lignin.
• General formula (1) shows a C 6 -C 3 unit, which is a partial structure of lignin. That is, the reaction indicated by the arrow on the left introduces a sulfonic acid (salt) group at the ⁇ -position, and is generally called sulfonation.
• a sulfonic acid (salt) group is introduced to the 5-position of the aromatic nucleus via formaldehyde in addition to the ⁇ -position.
• M represents a hydrogen atom, a monovalent metal salt, or a divalent metal salt
• Sulfomethylated kraft lignin may be produced by a known method, for example, by reacting kraft lignin with sulfites and aldehydes.
• the amount of sulfite added is preferably more than 16.0% by mass and 25.0% by mass or less relative to the amount of lignin solids, and more than 16.0% by mass and 23.0% by mass or less more preferred. If the amount of sulfite to be added is less than the above range, the sulfone groups may not be sufficiently introduced into the lignin, and the capacity, discharge characteristics and life may deteriorate. On the other hand, when sulfite is added excessively, it may remain as an unreacted product, and the lignin purity may be lowered, thereby deteriorating charge acceptance, capacity, and discharge characteristics.
• Formaldehyde is preferable as the aldehyde.
• the amount of aldehyde to be added is preferably more than 4.0% by weight and less than 6.6% by weight, more than 4.0% by weight and less than 6.1% by weight with respect to the lignin solids content. preferable. If the amount of formaldehyde is not within the above range, the sulfone groups may not be sufficiently introduced into the lignin, and the capacity, discharge characteristics and life may deteriorate.
• the weight average molecular weight of the sulfomethylated kraft lignin used in the present invention is preferably 10,000 or more and 18,000 or less. If the weight-average molecular weight is larger than the above upper limit, there is a possibility that the charge acceptability will be deteriorated.
• the weight average molecular weight is measured by gel permeation chromatography (GPC).
• GPC measurement may be performed under the following conditions by a known method of pullulan conversion. Measuring device; manufactured by Tosoh Column used; Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: 1.0% Na tetraborate, 0.3% isopropyl alcohol aqueous solution Eluent flow rate: 1.00 mL/min Column temperature; 50°C Measurement sample concentration; 0.2% by mass Reference material: Pullulan (manufactured by Showa Denko) Detector; RI detector (manufactured by Tosoh) Calibration curve; pullulan standard
• the organic shrinkage inhibitor of the present invention is mainly added to the negative electrode plate of lead-acid batteries.
• the addition ratio of the solid content of the organic shrink-proofing agent is usually 0.02 to 1.0% by mass based on the lead powder.
• a lead-acid battery using the organic anti-shrinking agent for lead-acid batteries of the present invention can be used for automobile batteries, portable equipment batteries, computer backup batteries, communication batteries, and the like.
• ⁇ Cyclic voltammetry method Examples in the present invention were carried out by cyclic voltammetry (CV) using a three-electrode system of a working electrode, a counter electrode and a reference electrode.
• CV cyclic voltammetry
• a CV curve horizontal axis: potential, vertical axis: current
• the potential of the electrode is scanned positively, electron transfer occurs from the reductant near the electrode, and an oxidation current flows.
• the oxidation current decreases and forms an upwardly convex peak in the CV curve.
• Kraft lignin was separated by a known method. That is, carbon dioxide was passed through conifer (N material) kraft cooking black liquor to lower the pH of the black liquor to 10, and primary filtration was performed. It was re-dispersed in water again, lowered to pH 2 with sulfuric acid, subjected to secondary filtration, washed with water and dried to obtain N material kraft lignin.
• ⁇ Production Example 2 500 parts of a solution of N material kraft lignin dissolved in NaOH to a pH of 10 to a solids content of 12%, 12.0 parts of sodium sulfite, and a 37% formaldehyde solution in a glass reaction vessel equipped with a thermometer, stirrer and reflux apparatus8. 5 parts were charged and reacted at 90° C. for 10 hours while stirring. After cooling to room temperature, N material sulfomethylated kraft lignin (A-2) was obtained.
• Vanillex N (hereinafter referred to as B-1, manufactured by Nippon Paper Industries Co., Ltd., concentration 95%, main component: partially desulfonated sulfite lignin) was used.
• ⁇ Comparative Example 3 500 parts of a solution of N material kraft lignin dissolved in NaOH to a pH of 10 to a solid content of 17%, 8.5 parts of sodium sulfite, and a 37% formaldehyde solution in a 1 L autoclave equipped with a thermometer, stirrer and reflux condenser6. 0 part was charged and reacted at 130° C. for 120 minutes while stirring. After cooling to room temperature, N material sulfomethylated kraft lignin (B-3) was obtained.
• ⁇ Comparative Example 6> Precipitated kraft lignin was obtained from hardwood kraft cooking black liquor instead of softwood kraft cooking black liquor following the method described in the examples of WO2012/005677.
• the resulting precipitated kraft lignin was dissolved in 48% NaOH to obtain a kraft lignin solution having a pH of 10 and a solid content concentration of 20%.
• 100 parts of the resulting kraft lignin solution 400 parts of water, 7.0 parts of 37% formaldehyde solution (manufactured by Wako Pure Chemical Industries), sodium sulfite Kojunyaku Co., Ltd.) was charged, and the temperature was raised to 140° C. while stirring.
• Table 1 shows the compositions of the sulfomethylated kraft lignin obtained in Production Examples 1-8, the partially desulfonated sulfite lignin of Comparative Example 1, and the sulfomethylated kraft lignin of Comparative Examples 2-7.
• % in Table 1 represents mass % with respect to the solid content of the composition obtained in each production example.
• the amount of discharge in the cycle in which the amount of charge and discharge reached the maximum value was determined as the maximum amount of discharge, and used as an index of the capacity/discharge characteristics.
• the value obtained by dividing the maximum value of the charging current in the CV curve at the 2,000th cycle by the amount of charge was defined as the charge acceptability.
• % in Table 2 represents the performance difference when the performance of Comparative Example 1 (B-1) is taken as 100%.
• Examples 1 to 8 (A-1 to A-8) included in the scope of the organic expander for lead-acid batteries of the present invention are Comparative Examples 1 to 6 (B-1 to B-6).
• the charge acceptance of Examples 1 to 8 (A-1 to A-8) included in the scope of the organic anti-shrinking agent for lead-acid batteries of the present invention was lower than that of the organic anti-shrinking agent for lead-acid batteries of Comparative Example 1 (B-1). Although it may be slightly lower than the agent, it is within 5% and improved compared to the organic anti-shrinking agent for lead-acid batteries of Comparative Example 7 (B-7).

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Compounds Of Unknown Constitution (AREA)
• Phenolic Resins Or Amino Resins (AREA)

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• 2022
  • 2022-10-25 CN CN202280075991.2A patent/CN118202492A/zh active Pending
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  • 2022-10-25 EP EP22898295.5A patent/EP4439732A4/en active Pending
  • 2022-10-25 WO PCT/JP2022/039606 patent/WO2023095511A1/ja not_active Ceased
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