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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/627—Expanders 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/005—Lignin
• • 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 a lead-acid battery, it improves the low-temperature rapid discharge performance and suppresses sulfation. There is a problem of declining performance.
• An object of the present invention is to provide an organic shrinkage agent that maintains the charge acceptance of the lead-acid battery described above and has an excellent balance of life, capacity, and discharge characteristics.
• the organic expander for lead-acid batteries according to (1) which has a weight-average molecular weight of 16,000 or less.
• the organic shrink-proofing agent for lead-acid batteries according to [1] wherein the organic S content is 1.5 to 3.0% by mass and the weight-average molecular weight is 16,000 or less.
• an organic anti-shrinking agent that maintains the charge acceptability of a lead-acid battery and has an excellent balance of life, capacity, and discharge characteristics.
• 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 is 1.5 to 3.8% by mass.
• 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 1.5 to 3.8% by mass, more preferably 1.5 to 3.0% by mass. If the organic S content is too much more than the above upper limit, charge acceptance may deteriorate, and if the organic S content is too less than the above lower limit, capacity, discharge characteristics, and life may deteriorate.
• 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 2.0 to 16.0% by mass, more preferably 2.0 to 11.0% by mass, based on the amount of lignin solids. If the amount of sulfite added is less than the above range, no sulfone groups are introduced into the lignin. On the other hand, if the sulfite is added excessively, excessive sulfone groups may be introduced into the lignin, deteriorating charge acceptance.
• Formaldehyde is preferable as the aldehyde.
• the amount of aldehyde to be added is preferably 0.5 to 4.0% by mass, more preferably 0.5 to 3.0% by mass, based on the lignin solids content. If the amount of formaldehyde is outside the above range, no sulfone groups are introduced into the lignin.
• the weight average molecular weight of the sulfomethylated kraft lignin used in the present invention is preferably 8,000 or more and 16,000 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 anti-shrinking 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 vertical axis: potential, horizontal 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.
• N material kraft lignin was dissolved at pH 10 with NaOH so that the solid content was 17% to obtain N material kraft lignin solution (B-1).
• 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.
• Vanillex N (hereinafter referred to as B-5, manufactured by Nippon Paper Industries Co., Ltd., concentration 95%, main component: partially desulfonated sulfite lignin) was used.
• Table 1 shows the compositions of the sulfomethylated kraft lignins obtained in Production Examples 1-7 and the kraft lignins, sulfomethylated kraft lignins, and partially desulfonated sulfite lignins of Comparative Examples 1-5.
• % in Table 1 represents mass % with respect to the solid content of the composition obtained in each production example.
• % in Table 2 represents the performance difference when the performance of Comparative Example 1 (B-1) is taken as 100%.
• Examples 1 to 4 (A-1 to A-4) included in the scope of the organic expander for lead-acid batteries of the present invention are Comparative Example 1 (B-1) and Comparative Example 2 (B- Compared to the organic anti-shrinking agent for lead-acid batteries of 2), the number of cycles at which the charge/discharge amount reaches a maximum and the maximum discharge amount were improved, and the charge acceptance was almost the same.
• Examples 1 to 4 are superior in charge acceptance compared to Comparative Examples 3 to 5 (B-3 to B-5). It was excellent in balance with acceptability.
• Examples 5 to 7 (A-5 to A-7) included in the scope of the organic expander for lead-acid batteries of the present invention are Comparative Example 1 (B-1) and Comparative Example 2 (B-2).
• the number of cycles at which the amount of charge and discharge is maximized, the maximum amount of discharge, and charge acceptance are all improved, and the charge acceptance is superior to Comparative Examples 3 to 5.
• the battery had an excellent balance between the number of cycles at which the charge/discharge amount was maximized, the maximum discharge amount, and the charge acceptability.

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• 2022
  • 2022-02-21 US US18/280,783 patent/US20240304821A1/en active Pending
  • 2022-02-21 EP EP22766792.0A patent/EP4306573A4/en active Pending
  • 2022-02-21 CN CN202280019472.4A patent/CN117063312A/zh active Pending
  • 2022-02-21 JP JP2023505263A patent/JPWO2022190829A1/ja active Pending
  • 2022-02-21 WO PCT/JP2022/006805 patent/WO2022190829A1/ja not_active Ceased
• 2023
  • 2023-12-15 JP JP2023211603A patent/JP2024019560A/ja active Pending

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