US20040151951A1 - Lithium based electrochemical cell systems - Google Patents
Lithium based electrochemical cell systems Download PDFInfo
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- US20040151951A1 US20040151951A1 US10/738,400 US73840003A US2004151951A1 US 20040151951 A1 US20040151951 A1 US 20040151951A1 US 73840003 A US73840003 A US 73840003A US 2004151951 A1 US2004151951 A1 US 2004151951A1
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- cell system
- blend
- agent comprises
- degassing agent
- lithium
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 35
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000007872 degassing Methods 0.000 claims description 19
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 8
- DCRYNQTXGUTACA-UHFFFAOYSA-N 1-ethenylpiperazine Chemical compound C=CN1CCNCC1 DCRYNQTXGUTACA-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- -1 aromatic carbonates Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 4
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 claims description 4
- SOKHGJZTJQMHEW-UHFFFAOYSA-N 2,3-dimethylpenta-1,4-diene Chemical compound C=CC(C)C(C)=C SOKHGJZTJQMHEW-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- MZNSQRLUUXWLSB-UHFFFAOYSA-N 2-ethenyl-1h-pyrrole Chemical compound C=CC1=CC=CN1 MZNSQRLUUXWLSB-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011244 liquid electrolyte Substances 0.000 claims description 3
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 claims description 2
- 229910007042 Li(CF3SO2)3 Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910010584 LiFeO2 Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910015726 LiMn0.3Co0.3Ni0.3O2 Inorganic materials 0.000 claims description 2
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 claims description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 claims description 2
- 229910016130 LiNi1-x Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 23
- 230000000996 additive effect Effects 0.000 abstract description 6
- 230000001629 suppression Effects 0.000 abstract description 4
- 239000005518 polymer electrolyte Substances 0.000 abstract description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004299 exfoliation Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- Gas generation in both Li-ion and lithium-metal based primary and secondary electrochemical cells may become a serious problem both during normal cell operation at room temperature and, more especially, at elevated temperatures.
- the consequence of gas build up includes cell can expansion and subsequent can rupture, leading to cell and or battery failure.
- the gassing problem has been observed to be extremely serious in large electric vehicle type cell systems and in pouch type cell systems where rupture of the cell containment leads to serious safety problems.
- the gassing problem is also very serious in lithium-metal based primary cells using liquid and/or solid electrolytes in vivo applications such as for heart pacemakers and similar devices.
- This invention is directed toward the development of both primary and secondary Li-ion and lithium-metal based electrochemical cell systems in which the suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of the respective cell, or to the cell whether it be a liquid, a solid- or plastized polymer electrolyte system.
- the gas suppression additives in this patent application are primarily based on unsaturated hydrocarbons and nitrogen containing organic materials.
- FIG. 1 shows cycle life characteristics of a Li-ion cell (ANL-1) containing 1.0 wt % 2,3 dimethyl-1,3 butadiene with the 1 M LiPF 6 dissolved in ethylene carbonate (30%) and ethyl-methyl carbonate (70%);
- FIG. 2 shows cycle life characteristics of a Li-ion cell (ANL-2) containing 2.0 wt % VEC and 1.0 wt % 2,3 dimethyl-1,3 butadiene with the 1 M LiPF 6 dissolved in ethylene carbonate (20%), propylene carbonate (20%), and diethyl carbonate (60%); and
- FIG. 3 shows changes of gas pressure change during ARC measurements of negative electrodes and electrolytes from Li-ion (ANL-1) cells with additives and a reference cell negative electrode and electrolyte from a (ANL-1) cell, but without additives.
- the primary and secondary electrochemical Li-ion cells of this invention have minimal gassing and possess high specific energy and power, as well as excellent calendar and cycle life across a broad temperature range.
- the additives that are capable of ameliorating gas generation in the lithium based electrochemical cells include at least the following class of organic compounds, which will be described in more detail hereinafter: (a) CH 2 ⁇ R 1 ⁇ CH 2 , where R 1 is an aliphatic carbon chain of 1 to 7 carbons, either linear or branched (b) CH ⁇ R 1 ⁇ CH, (c) CH 2 ⁇ R 1 , (d) CH ⁇ R 1 , (e) R 2 —CH ⁇ R 1 ⁇ CH 2 , where R 2 is an aromatic (toluene or benzene), a cyclic hydrocarbon, (f) R 2 —C ⁇ R 1 ⁇ CH, (g) R 2 —CH ⁇ R 1 , (h) R 2 —C ⁇ R 1 , (i) st
- the present invention provides electrochemical lithium-based primary and secondary cells with excellent calendar life across a broad temperature, and includes cells with liquid and solid- and plastized polymer electrolytes.
- FIG. 1 shows the improved cycle life characteristics of a Li-ion cell (ANL-1) containing 1.0 wt % 2,3 dimethyl-1,3 butadiene (DMB).
- the cell utilized a crystalline graphite anode, a LiNi 0.8 Co 0.2 O 2 cathode and an electrolyte containing 1 M LiPF 6 dissolved in a blend of ethylene carbonate and ethyl-methyl carbonate.
- FIG. 2 shows the improved cycle life characteristics of a Li-ion cell (ANL-2) containing 2.0 wt % VEC and 1.0 wt % 2,3 dimethyl-1,3 butadiene with the 1 M LiPF 6 dissolved in blend of ethylene carbonate, propylene carbonate, and dimethyl carbonate.
- the cell utilized the same cathode and anode as cell (ANL-1).
- FIG. 3 shows the gas pressures developed by studies of the respective negative electrodes with electrolyte from cell (ANL-1) and compares the pressures developed by the negative electrodes and electrolyte from a similar cell that did not contain the 2,3 dimethyl-1,3 butadiene.
- the results of these studies indicate the additives significantly reduce the degree of gassing in the negative electrodes of cell (ANL-1), as compared to the negative electrode/electrolyte gassing from a similar cell but without the additive package.
- the additive effects in reducing pressure buildup are especially effective with the negative electrodes.
- the additives were also found to increase the activation energy and decrease the heat of reaction around the onset temperature that is believed to be the onset temperature for thermal runaway in the commercial lithium ion cells. The result of these studies indicate that these additives may be very effective in reducing gas buildup in high energy lithium-based cells for many different applications such as electric and hybrid vehicles, as well as in vivo applications such as for heart pacemakers and other implantable devices for the human body.
- lithium electrochemical cell systems include:
- a secondary Li-ion cell comprising a lithium metal oxide positive electrode, a negative electrode containing a crystalline carbon like graphite, an electrolyte composed of a lithium salt, and a blend of at least two aprotic solvents.
- the solvents include ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, or diethyl carbonate, and finally a compound that reduces cell gassing.
- the salts include LiPF 6 , LiBF 4 , LiAsF 6 , and other salts currently being used or being developed such as the lithium bisoxlatoborate (LiBOB) salts.
- These electrolytes also contain a degassing agent.
- a lithium-metal based primary or secondary electrochemical cell This cell is similar to those described above except that they use lithium metal as the negative electrode, a metal oxide positive electrode such as LiCoO 2 , LiNiO 2 , LiNi 1-x Co y Me z O 2 , LiMn 0.5 Ni 0.5 O 2 , LiMn 0.3 Co 0.3 Ni 0.3 O 2 , LiFePO 4 , LiMn 2 O 4 , LiFeO 2 , LiMc 0.5 Mn 1.5 O 4 , vanadium oxide, and mixtures thereof, wherein Me is Al, Mg, Ti, B, Ga, or Si, and Mc is a divalent metal such as Fe, Co, Cu, Cr and Ni, and either a liquid electrolyte described in (i) liquid or solid polymer or plastized electrolyte described in cell types (ii) above and that contains a degassing agent.
- a metal oxide positive electrode such as LiCoO 2 , LiNiO 2 , LiNi 1-x Co
- the agents or additives described herein include the following class of organic compounds; (a) CH 2 ⁇ R 1 ⁇ CH 2 , where R 1 is an aliphatic carbon chain of 1 to 7 carbons, either linear or branched (b) CH ⁇ R 1 ⁇ CH, (c) CH 2 ⁇ R 1 , (d) CH ⁇ R 1 , (e) R 2 —C ⁇ R 1 ⁇ CH 2 , where R 2 is an aromatic (toluene or benzene), a cyclic hydrocarbon, a pyrrole, a piperazine, or a piperidine molecule, (f) R 2 —C ⁇ R 1 ⁇ CH, (g) R 2 —CH ⁇ R 1 , (h) R 2 —C ⁇ R 1 , (i) styrene carbonate, (j) aromatic carbonates, (k) vinyl pyrrole, (l) vinyl piperazine, (m) vinyl piperidine, (n) vinyl pyridine (o) triphenyl
- the agents or additives described herein can include, for example, 2,3 dimethyl-1,3 butadiene, 1,3 butadiene, is 2,3 dimethyl-1,4 pentadiene, 1,5 hexadiene, a blend of 2,3 dimethyl-1,3 butadiene and vinyl ethylene carbonate, and a blend of 2,3 dimethyl-1,4 pentadiene and vinyl pyridine.
- additives or agents include a blend of 1,5 hexadiene and piperazine, a blend of 2,3 dimethyl-1,3 butadiene and styrene, a blend of 2,3 dimethyl-1,3 butadiene and piperidine, a blend of hexadiene and vinyl pyridine, a blend of 2,3 dimethyl-1,3 butadiene and triphenyl phosphate, a blend of 2,3 dimethyl-1,3 butadiene and vinyl pyridine, styrene carbonate, and a blend of styrene carbonate and vinyl piperazine.
- the additive or agent can also be a blend of two or more of the additives described above. According to one embodiment of the invention, the total concentration of additives ranges from 0.1 to 25 wt %, with an optimum concentration varying from 0.1 to 10 wt %.
Abstract
Description
- This application claims priority to U.S. Provisional Patent Application No. 60/434,214, filed on Dec. 17, 2002 and incorporated herein by reference.
- [0002] This invention was made with government support under Contract No. W-31-109-ENG-38 awarded to the Department of Energy. The Government has certain rights in this invention.
- Gas generation in both Li-ion and lithium-metal based primary and secondary electrochemical cells may become a serious problem both during normal cell operation at room temperature and, more especially, at elevated temperatures. The consequence of gas build up includes cell can expansion and subsequent can rupture, leading to cell and or battery failure. For example, the gassing problem has been observed to be extremely serious in large electric vehicle type cell systems and in pouch type cell systems where rupture of the cell containment leads to serious safety problems. The gassing problem is also very serious in lithium-metal based primary cells using liquid and/or solid electrolytes in vivo applications such as for heart pacemakers and similar devices.
- Because both the negative and positive electrodes in the charged states of nearly all lithium based electrochemical cell systems are thermodynamically unstable in respect to the electrolyte, it is especially important that electrolyte additives be developed to stabilize the electrodes by decreasing the kinetics of the respective electrode reactions and thereby reducing the gas generation.
- This invention is directed toward the development of both primary and secondary Li-ion and lithium-metal based electrochemical cell systems in which the suppression of gas generation is achieved through the addition of an additive or additives to the electrolyte system of the respective cell, or to the cell whether it be a liquid, a solid- or plastized polymer electrolyte system. The gas suppression additives in this patent application are primarily based on unsaturated hydrocarbons and nitrogen containing organic materials.
- FIG. 1 shows cycle life characteristics of a Li-ion cell (ANL-1) containing 1.0 wt % 2,3 dimethyl-1,3 butadiene with the 1 M LiPF6 dissolved in ethylene carbonate (30%) and ethyl-methyl carbonate (70%);
- FIG. 2 shows cycle life characteristics of a Li-ion cell (ANL-2) containing 2.0 wt % VEC and 1.0 wt % 2,3 dimethyl-1,3 butadiene with the 1 M LiPF6 dissolved in ethylene carbonate (20%), propylene carbonate (20%), and diethyl carbonate (60%); and
- FIG. 3 shows changes of gas pressure change during ARC measurements of negative electrodes and electrolytes from Li-ion (ANL-1) cells with additives and a reference cell negative electrode and electrolyte from a (ANL-1) cell, but without additives.
- By use of appropriate additive or additives, the primary and secondary electrochemical Li-ion cells of this invention have minimal gassing and possess high specific energy and power, as well as excellent calendar and cycle life across a broad temperature range. The additives that are capable of ameliorating gas generation in the lithium based electrochemical cells include at least the following class of organic compounds, which will be described in more detail hereinafter: (a) CH2═R1═CH2, where R1 is an aliphatic carbon chain of 1 to 7 carbons, either linear or branched (b) CH≡R1≡CH, (c) CH2═R1, (d) CH≡R1, (e) R2—CH═R1═CH2, where R2 is an aromatic (toluene or benzene), a cyclic hydrocarbon, (f) R2—C≡R1≡CH, (g) R2—CH═R1, (h) R2—C≡R1, (i) styrene carbonate, (j) aromatic carbonates, (k) vinyl pyrrole, (l) vinyl piperazine, (m) vinyl piperidine, (n) vinyl pyridine, (o) triphenyl phosphate and blends thereof. These blends may involve other additives such as vinyl ethylene carbonate to protect against exfoliation in propylene carbonate based Li-ion electrolyte systems.
- The present invention provides electrochemical lithium-based primary and secondary cells with excellent calendar life across a broad temperature, and includes cells with liquid and solid- and plastized polymer electrolytes.
- FIG. 1 shows the improved cycle life characteristics of a Li-ion cell (ANL-1) containing 1.0 wt % 2,3 dimethyl-1,3 butadiene (DMB). The cell utilized a crystalline graphite anode, a LiNi0.8Co0.2O2 cathode and an electrolyte containing 1 M LiPF6 dissolved in a blend of ethylene carbonate and ethyl-methyl carbonate.
- FIG. 2 shows the improved cycle life characteristics of a Li-ion cell (ANL-2) containing 2.0 wt % VEC and 1.0 wt % 2,3 dimethyl-1,3 butadiene with the 1 M LiPF6 dissolved in blend of ethylene carbonate, propylene carbonate, and dimethyl carbonate. The cell utilized the same cathode and anode as cell (ANL-1).
- FIG. 3 shows the gas pressures developed by studies of the respective negative electrodes with electrolyte from cell (ANL-1) and compares the pressures developed by the negative electrodes and electrolyte from a similar cell that did not contain the 2,3 dimethyl-1,3 butadiene. The results of these studies indicate the additives significantly reduce the degree of gassing in the negative electrodes of cell (ANL-1), as compared to the negative electrode/electrolyte gassing from a similar cell but without the additive package. The additive effects in reducing pressure buildup are especially effective with the negative electrodes. The additives were also found to increase the activation energy and decrease the heat of reaction around the onset temperature that is believed to be the onset temperature for thermal runaway in the commercial lithium ion cells. The result of these studies indicate that these additives may be very effective in reducing gas buildup in high energy lithium-based cells for many different applications such as electric and hybrid vehicles, as well as in vivo applications such as for heart pacemakers and other implantable devices for the human body.
- According to one embodiment of the invention, lithium electrochemical cell systems include:
- (i) A secondary Li-ion cell comprising a lithium metal oxide positive electrode, a negative electrode containing a crystalline carbon like graphite, an electrolyte composed of a lithium salt, and a blend of at least two aprotic solvents. The solvents include ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, or diethyl carbonate, and finally a compound that reduces cell gassing. The salts include LiPF6, LiBF4, LiAsF6, and other salts currently being used or being developed such as the lithium bisoxlatoborate (LiBOB) salts.
- (ii) A Li-ion secondary electrochemical cell similar to the cell type (i) described above except that the electrolyte is either a liquid gel or solid polymer with a dissolved salt such as LiClO4, LiPF6, LiBF4, LiAsF6, LiCF3SO3, Li(CF3SO2)2N, Li(CF3SO2)3C, LiN(SO2C2F5)2, lithium alkyl fuorophosphate, lithium bis(chelato)borates and mixtures thereof; or a solid polymer blended with the electrolyte described above in cell type (i), called a plastized electrolyte. These electrolytes also contain a degassing agent.
- (iii) A lithium-metal based primary or secondary electrochemical cell. This cell is similar to those described above except that they use lithium metal as the negative electrode, a metal oxide positive electrode such as LiCoO2, LiNiO2, LiNi1-xCoyMezO2, LiMn0.5Ni0.5O2, LiMn0.3Co0.3Ni0.3O2, LiFePO4, LiMn2O4, LiFeO2, LiMc0.5Mn1.5O4, vanadium oxide, and mixtures thereof, wherein Me is Al, Mg, Ti, B, Ga, or Si, and Mc is a divalent metal such as Fe, Co, Cu, Cr and Ni, and either a liquid electrolyte described in (i) liquid or solid polymer or plastized electrolyte described in cell types (ii) above and that contains a degassing agent.
- The agents or additives described herein include the following class of organic compounds; (a) CH2═R1═CH2, where R1 is an aliphatic carbon chain of 1 to 7 carbons, either linear or branched (b) CH≡R1≡CH, (c) CH2═R1, (d) CH≡R1, (e) R2—C═R1═CH2, where R2 is an aromatic (toluene or benzene), a cyclic hydrocarbon, a pyrrole, a piperazine, or a piperidine molecule, (f) R2—C≡R1≡CH, (g) R2—CH═R1, (h) R2—C≡R1, (i) styrene carbonate, (j) aromatic carbonates, (k) vinyl pyrrole, (l) vinyl piperazine, (m) vinyl piperidine, (n) vinyl pyridine (o) triphenyl phosphate, (p) and blends thereof. These blends may involve other additives, such as vinyl ethylene carbonate, to protect against exfoliation in propylene carbonate based Li-ion electrolyte systems.
- The agents or additives described herein can include, for example, 2,3 dimethyl-1,3 butadiene, 1,3 butadiene, is 2,3 dimethyl-1,4 pentadiene, 1,5 hexadiene, a blend of 2,3 dimethyl-1,3 butadiene and vinyl ethylene carbonate, and a blend of 2,3 dimethyl-1,4 pentadiene and vinyl pyridine. Other additives or agents include a blend of 1,5 hexadiene and piperazine, a blend of 2,3 dimethyl-1,3 butadiene and styrene, a blend of 2,3 dimethyl-1,3 butadiene and piperidine, a blend of hexadiene and vinyl pyridine, a blend of 2,3 dimethyl-1,3 butadiene and triphenyl phosphate, a blend of 2,3 dimethyl-1,3 butadiene and vinyl pyridine, styrene carbonate, and a blend of styrene carbonate and vinyl piperazine. Additionally, the additive or agent can also be a blend of two or more of the additives described above. According to one embodiment of the invention, the total concentration of additives ranges from 0.1 to 25 wt %, with an optimum concentration varying from 0.1 to 10 wt %.
- It should be understood that the above description of the invention and the specific examples and embodiments therein, while indicating the preferred embodiments of the present invention, are given only by demonstration and not limitation. Many changes and modifications within the scope of the present invention may therefore be made without departing from the spirit of the invention, and the invention includes all such changes and modifications.
Claims (20)
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US11094925B2 (en) | 2017-12-22 | 2021-08-17 | Zenlabs Energy, Inc. | Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance |
US11742474B2 (en) | 2017-12-22 | 2023-08-29 | Zenlabs Energy, Inc. | Electrodes with silicon oxide active materials for lithium ion cells achieving high capacity, high energy density and long cycle life performance |
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US8168325B2 (en) | 2012-05-01 |
US20080070121A1 (en) | 2008-03-20 |
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