CN1053513A - With the complex Li-Mn-oxide is anodal all solid-state lithium battery - Google Patents

With the complex Li-Mn-oxide is anodal all solid-state lithium battery Download PDF

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Publication number
CN1053513A
CN1053513A CN91107336A CN91107336A CN1053513A CN 1053513 A CN1053513 A CN 1053513A CN 91107336 A CN91107336 A CN 91107336A CN 91107336 A CN91107336 A CN 91107336A CN 1053513 A CN1053513 A CN 1053513A
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solid
oxide
state lithium
electrolyte
complex
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CN91107336A
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CN1023166C (en
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吴浩青
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Fudan University
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Fudan University
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to electrochemical field, is a kind ofly can fill the formula all solid-state lithium battery again.Its anode adopts lithium material, and negative electrode adopts complex Li-Mn-oxide, and electrolyte adopts modification organolithium montmorillonite, and the double as diaphragm material.This battery repeatedly degree of depth charges and discharge, and has good electrical properties, and in light weight, volume is little, easy to use.

Description

With the complex Li-Mn-oxide is anodal all solid-state lithium battery
The invention belongs to electrochemical field, is a kind of storage battery.
Common storage battery has lead acid accumulator and nickel-cadmium cell etc. at present.The former weight is big, specific energy is little; Latter's electrical property is better.Both are not all-solid-state batteries all, and liquid electrolyte flows out easily during use, and storage life is shorter, cause certain limitation to use.
The applicant is in " manganese dioxide accumulator of all solid lithium spinel structure " (application number 89107578) of application on September 23rd, 1989, and electrolyte adopts montmorillonite, and its conductivity is high not enough.The anodal LiMn204 that adopts, the discharge voltage of battery has a step that differs about 1 volt, makes designed operating voltage can only utilize a wherein part, thereby electric capacity is reduced.
The purpose of this invention is to provide a kind of good electrical property, in light weight, specific energy is big can fill the formula full solid-state accumulator again.
The present invention includes anode, negative electrode, electrolyte, shell several sections.Fig. 1 is its structural representation.Anode 1(negative pole wherein) adopt lithium (Li) material, negative electrode 2 adopts complex Li-Mn-oxide (Li 2OMnO 2) material; Electrolyte 3 adopts modified montmorillonite used or poly(ethylene oxide) lithium perchlorate (PEO 8LiClO 4), or other ionic conduction thing.Above-mentioned anode 1 is pressed in the nickel current collection by lithium and constitutes on the net; Above-mentioned negative electrode (positive pole) 2 by complex Li-Mn-oxide be pressed in the nickel current collection after acetylene black, polytetrafluoroethylene mix and constitute on the net, the ratio of its mixing and technology and conventional battery are made roughly the same, above-mentioned electrolyte 3 is solid-state, thereby double as barrier film again, saved diaphragm material required when adopting liquid electrolyte.Anode cover and have sealing ring 4 to do the isolation of anode and negative electrode on every side between shell.With above-mentioned anode, negative electrode, solid electrolyte and sealing ring routinely technology envelope be pressed in the shell 5, promptly get full solid-state accumulator.
Negative electrode of the present invention (positive pole) material-complex Li-Mn-oxide is the embedding compound (abbreviation block polymer) of lithium in the complex Li-Mn-oxide with a fixed structure, it is a kind of good energy-accumulating material, its X-ray diffraction diagram is composed as shown in Figure 3, and its characteristic peak is listed as follows:
Peak number 2 θ peak value peaks number 2 θ peak values
1 18.71 301 7 49.01 34?
2 28.65 321 8 56.67 266
3 37.33 402 9 59.03 122
4 40.98 74 10 64.97 129
5 42.82 151 11 67.38 65
6 44.6 197
Solid electrolyte modification hectorite of the present utility model, obtain by embedding high polymer such as PPOX between montmorillonite layer, detailed process is: earlier the intermediary water of hectorite is removed, add polymer monomer then, as expoxy propane, interlayer is suctioned, the polymer monomer on flush away surface in centrifuge.Make catalyst with (0.5 ± 0.2) % lithium methoxide, in water-bath, heat, make it, promptly get modified montmorillonite used in the interlayer polymerization.Its conductivity is than the high 1-2 of a hectorite order of magnitude.
The mechanism that discharges and recharges of this battery is as follows: discharge, the lattice of lithium " embedding " positive electrode; Charging, lithium " takes off embedding " and comes out from lattice, and " embeddings " and " taking off embedding " reciprocation cycle in this way reach the purpose of energy storage.This battery can the degree of depth repeatedly charge and discharge, and cathode material structure does not change.So this storage battery has good electrical properties, and in light weight, volume is little, and is easy to use, and electrolyte can not outflow.
The present invention is because positive pole adopts complex Li-Mn-oxide, and its discharge curve is steady, operating voltage is 2.9 volts, and electric capacity increases.
The present invention can make button cell, and manufacture craft is identical with other button lithium batteries, and its structure such as Fig. 1 also can make cylindrical battery etc.
Embodiment: by structure shown in Figure 1, make storage battery with common process, its open circuit voltage is 3.2 volts, and with 300 μ A/cm2 discharge, operating voltage is 2.9 volts, but the degree of depth repeatedly charge and discharge, Fig. 2 is its 21st, 22,25 time discharge diagram that circulates.Wherein, black circle is represented the 21st secondary data, and soft dot is represented the 22nd time data, and the triangle form point is represented the 25th time data.Electric current I is 250 μ A.These data declarations, the invertibity of positive electrode.
Fig. 1 is the button cell structural representation.
Fig. 2 is the discharge curve of the 21st time, 22 times, 25 times circulations of this storage battery.
Fig. 3 is this battery cathode material Li 2O, MnO 2X-ray diffraction diagram spectrum.

Claims (4)

1, a kind of all solid-state lithium battery, comprise anode, negative electrode, solid electrolyte and shell, constitute with the conventional method encapsulation, anode adopts lithium material, it is characterized in that negative electrode (positive pole) adopts complex Li-Mn-oxide (Li2OMnO2), electrolyte adopts the modification hectorite that is obtained by embedding high polymer between montmorillonite layer.
2, all solid-state lithium battery according to claim 1 is characterized in that electrolyte is modified montmorillonite used for what obtained by embedding expoxy propane between montmorillonite layer.
3, according to claim 1 and 2 described all solid-state lithium batteries, it is characterized in that negative electrode by complex Li-Mn-oxide be pressed in the nickel current collection after acetylene black, polytetrafluoroethylene mix and constitute on the net.
4, according to claim 1 and 2 described all solid-state lithium batteries, it is characterized in that its solid electrolyte modification hectorite is obtained by following method: the intermediary water of removing hectorite earlier, the unit such as the expoxy propane that add high polymer then, interlayer is suctioned, flush away surface polymer monomer in centrifuge, make catalyst with (0.5 ± 0.2) % lithium methoxide, in water-bath, heat, make it in the interlayer polymerization.
CN91107336A 1991-03-05 1991-03-05 Full solid-state lithium storage battery using lithium-manganese compounded oxidate as positive elecrode Expired - Fee Related CN1023166C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN91107336A CN1023166C (en) 1991-03-05 1991-03-05 Full solid-state lithium storage battery using lithium-manganese compounded oxidate as positive elecrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN91107336A CN1023166C (en) 1991-03-05 1991-03-05 Full solid-state lithium storage battery using lithium-manganese compounded oxidate as positive elecrode

Publications (2)

Publication Number Publication Date
CN1053513A true CN1053513A (en) 1991-07-31
CN1023166C CN1023166C (en) 1993-12-15

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034704C (en) * 1993-03-03 1997-04-23 北京有色金属研究总院 Cathode of secondary battery and its prepn.
CN1061473C (en) * 1997-01-02 2001-01-31 中国科学院化学研究所 Lithium secondary cell and its preparing method
CN1061472C (en) * 1996-12-25 2001-01-31 中国科学院化学研究所 Carbon material for cathode of lithium secondry battery
CN1324738C (en) * 2002-02-25 2007-07-04 株式会社普利司通 Positive electrode for nonaqueous electrolyte battery, process for producing the same and nonaqueous electrolyte battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034704C (en) * 1993-03-03 1997-04-23 北京有色金属研究总院 Cathode of secondary battery and its prepn.
CN1061472C (en) * 1996-12-25 2001-01-31 中国科学院化学研究所 Carbon material for cathode of lithium secondry battery
CN1061473C (en) * 1997-01-02 2001-01-31 中国科学院化学研究所 Lithium secondary cell and its preparing method
CN1324738C (en) * 2002-02-25 2007-07-04 株式会社普利司通 Positive electrode for nonaqueous electrolyte battery, process for producing the same and nonaqueous electrolyte battery

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