US20120308876A1 - Rechargeable electrochemical cell - Google Patents

Rechargeable electrochemical cell Download PDF

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US20120308876A1
US20120308876A1 US13/578,110 US201113578110A US2012308876A1 US 20120308876 A1 US20120308876 A1 US 20120308876A1 US 201113578110 A US201113578110 A US 201113578110A US 2012308876 A1 US2012308876 A1 US 2012308876A1
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battery cell
cell according
electrolyte
sulfur dioxide
cell
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Guenther Hambitzer
Joachim Heitbaum
Claus Dambach
Martin Kampa
Christian Pszolla
Christiane Ripp
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FORTU INTELLECTUAL PROPERTY AG
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FORTU INTELLECTUAL PROPERTY AG
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    • H—ELECTRICITY
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    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a rechargeable electrochemical battery cell having a positive electrode, a negative electrode, and an electrolyte, the electrolyte containing sulfur dioxide (SO 2 ) and a conductive salt of the active metal of the cell.
  • SO 2 sulfur dioxide
  • the charge transport that is necessary for charging and discharging the cell is based on the mobility of the conductive salt ions in the electrolyte.
  • the electrolyte may be a liquid or a gel.
  • SO 2 electrolytes SO 2 -containing electrolytes
  • the SO 2 contributes to the mobility of the ions of the conductive salt that carry out this charge transport.
  • the SO 2 serves as a solvent of the conductive salt.
  • the electrolyte may contain another solvent to promote the mobility of the ions in the conductive salt, in addition to the SO 2 .
  • solvents may be inorganic solvents (for example sulfuryl chloride, thionyl chloride), organic solvents, and ionic liquids, which may be used individually or in a mixture.
  • an electrolyte solution is preferred that not only contains a SO 2 in low concentration as an additive, but in which the mobility of the conductive salt ions is provided mainly, preferably entirely, by the SO 2 .
  • SO 2 electrolytes offer considerable advantages (see “The Handbook of Batteries” by David Linden, 1994, McGraw Hill).
  • One of these advantages is that its conductivity is 5 to 10 times better than with organic electrolytes normally used in lithium ion battery cells. This enables higher charge and discharge currents, which in turn result in a high power density.
  • Good conductivity of the electrolyte is also advantageous with regard to the charge capacitance of the cell, because it allows use of relatively thick electrodes with high storage capacity for the active metal of the cell.
  • the various types of cells with SO 2 electrolyte differ from each other mainly with respect to the active metal and conductive salt used, and also with respect to the materials used for the positive and negative electrodes.
  • the present invention is directed in particular to battery cells having the following features:
  • It is an object of the invention is to provide battery cells with an SO 2 electrolyte that feature improved properties, in particular with regard to long-term operation with many charging and discharging cycles.
  • an electrochemical rechargeable battery cell having a housing, a positive electrode, a negative electrode, and an electrolyte, the electrolyte containing sulfur dioxide and a conductive salt of the active metal of the cell, which is characterized in that the total quantity of oxides contained in the cell that are able to react with sulfur dioxide and reduce the sulfur dioxide, is no more than 10 mMol for each Ah theoretical capacitance of the cell.
  • oxygen-containing contaminants can severely impair the long-term function of battery cells that include an electrolyte containing SO 2 .
  • These are oxygen-containing compounds that are able to react with and reduce the sulfur dioxide, that is to say, they are capable of such a reaction under the conditions that may occur during operational use of the battery.
  • Oxygen-containing compounds of such kind will be designated hereafter as “disturbing oxides”, as a non-limiting abbreviation.
  • the reactions at issue are often highly inhibited, so that they only take place over a very long period. However, in view of the fact that batteries must remain functional for long periods (several years), even such slow reactions still impair battery function.
  • a SubC size cell that was tested in the context of the invention has a theoretical discharge capacitance of 2.3 Ah.
  • the function of such a cell may be affected by as little as about 5 to 10 mMol disturbing oxide so severely that during long-term use, with many charging and discharging cycles, its capacitance goes down to zero.
  • the theoretical charge capacitance of the cell depends on its electrodes.
  • the theoretical capacitance of the positive electrode is taken to be the theoretical capacitance of the cell. This is the maximum theoretical charge of the active metal that can be stored in the electrode, i.e. the amount of electrical charge corresponding to the maximum quantity of active metal that the positive electrode may contain according to stoichiometric calculation. This value is always greater than the actually achievable maximum capacitance of the electrode (and thus also of the cell), because the charge amount that can theoretically be stored can never be fully drawn from the electrode in practice.
  • the cell's long-term function is significantly improved thereby.
  • the electrical charge capacitance remains essentially stable over many charging and discharging cycles.
  • Overcharging resistance is also significantly improved, i.e. the cell's function is not destroyed even by overcharging.
  • the invention primarily relates to cells with an electrolyte whose SO 2 content is so high that the mobility of the conductive salt ions is based mainly, or even entirely, on the presence of the SO 2 .
  • the minimum quantity of SO 2 per Ah theoretical capacitance of the cell is preferably 1 mMol, wherein a minimum quantity of 5 mMol is particularly preferred and a minimum quantity of 10 mMol is especially preferred, relative to the theoretical capacitance of the cell in each case.
  • a typical oxygen-containing contamination at the active material of a negative carbon electrode is C 6 O. It reacts with the LiC 6 of the electrode and the SO 2 of the electrolyte, consuming six electrons (e ⁇ ) according to the following reaction equation:
  • the reaction products are carbon (C 6 ), lithium thiosulfate (Li 2 S 2 O 3 ) and lithium oxide (Li 2 O).
  • the superscripted Roman numerals in parentheses indicate the oxidation number of the sulfur in the respective compound.
  • the oxidation number of the sulfur is lowered by 2 during the reaction.
  • the sulfur dioxide is thus reduced as the lithium thiosulfate is formed.
  • the lithium oxide formed in reaction equation (1) reacts with aluminum chloride (AlCl 3 ), a Lewis acid that is usually present in the electrolyte as a result of the autodissociation of the conductive salt, to produce aluminum oxychloride (AlOCl) and lithium chloride (LiCl).
  • AlOCl aluminum oxychloride
  • LiCl lithium chloride
  • the neutral form of the conductive salt (LiAlCl 4 ) may result in the dissolution of the Li 2 O and further reaction with Li 2 S 2 O 4 :
  • lithium dithionite Li 2 S 2 O 4
  • This compound of the covering layer reacts further according to (3a). SO 2 in the lithium dithionite is in turn reduced (the oxidation number of the sulfur is lowered from +III to +III), and lithium thiosulfate is formed.
  • reaction (4a) does not take place. In this case, the charge consumption is lowered to 14e ⁇ . This means that 378 mAh charge are irreversibly consumed for every mMol C 6 O.
  • the capacitance loss due to disturbing oxides at the active material of the negative electrode is thus between 162 and 564 mAh, depending on the solubility of the mentioned components, (which is also affected by temperature and SO 2 concentration, among other factors).
  • a typical oxygen-containing contamination at the active material of the positive electrode is a hydroxide that forms on the surface thereof.
  • a lithium metal oxide electrode of the general formula LiMeO 2 it may, for example, be LiMeO(OH) 2 . It reacts with the AlCl 3 in the electrolyte according to the following reaction equation to form aluminum oxychloride, a chloride of the metal Me, HCl, and LiCl:
  • the hydroxide may also react with the neutral form of the conductive salt in accordance with:
  • LiMeO(OH) 2 results in the consumption of 12 SO 2 molecules and 24 e ⁇ , while 6 molecules of Li 2 S 2 O 3 and 2 molecules of HCl are formed (with 3 molecules of AlOCl formed as an intermediate product).
  • the charge consumption is equivalent to a charge quantity of 702 mAh for every mMOl LiMeO(OH) 2 .
  • the lithium in one molecule of LiMeO(OH) 2 is no longer available as an active metal. This represents a further capacitance loss of 27 mAh per mMol LiMeO(OH) 2 .
  • the charge consumption is correspondingly reduced in this case as well, to 4 e ⁇ . This is equivalent to 108 mAh.
  • the current collectors to and from the electrodes are often made from nickel or a nickel alloy.
  • the surface of these components may be oxidized, that is to say, it may contain nickel oxide. If this nickel oxide has not (yet) been dissolved in the electrolyte solution, a direct reaction similar to reaction equation (1) may occur, producing Li 2 S 2 O 3 when the cell is charged.
  • Examples of final products with oxidation number ⁇ II are metal sulfides (such as Li 2 S ( ⁇ II) or Al 2 S ( ⁇ II) 3 ).
  • An example of a final product with oxidation number +VI is lithium chlorosulfonate (LiSO 3 Cl).
  • the preceding explanations show that the presence of disturbing oxides leads to the formation of a sulfur-oxygen compound when a cell is charged and discharged normally (without overcharging), and the sulfur in this compound may reach a maximum oxidation number of +111.
  • a sulfur-oxygen compound when a cell is charged and discharged normally (without overcharging), and the sulfur in this compound may reach a maximum oxidation number of +111.
  • One important example is a thiosulfate of the active metal (in the case of a lithium cell lithium thiosulfate).
  • sulfur dioxide in the electrolyte is reduced. If the cell is overcharged, giving rise to overcharge products, further reactions follow in which the sulfur of the thiosulfate is disproportionated to form sulfur compounds having oxidation numbers ⁇ II and +VI.
  • a characteristic reaction product that is formed if the cell is overcharged in the presence of disturbing oxides is a chlorosulfonate of the active metal. In a lithium cell, this is lithium chlorosulfonate.
  • the electrical charge quantity required for these reactions is provided by the cell, and is no longer available as usable battery capacitance.
  • the disturbing oxides named in the preceding are to be understood as exemplary of all types of disturbing oxides (in the sense of the definition provided above) that are present on or in the cell materials.
  • the positive electrode may contain disturbing oxides in the form of various oxide-containing compounds present on the surface of the electrode material. These include hydroxides (including water), oxide dihydroxides, carbonates, borates, and others.
  • the formula C 6 O serves as a simplified representation of an oxygen that is bound to a negative carbon electrode.
  • the graphite surface contains covalently bonded oxygen, for example as ketones, aldehydes, carbonyls, alcohols, epoxides, carboxylic acids, and others.
  • the oxygen may also be present as adsorbed water or adsorbed metal hydroxide or similar.
  • a common property of all disturbing oxides is that they are able to react with the sulfur dioxide in the electrolyte, reducing the sulfur dioxide.
  • a sulfur-oxygen compound is typically formed in which the sulfur has a maximum oxidation level of III, for example a thiosulfate of the active metal.
  • a sulfur-oxygen compound is typically produced that also contains a halogen, and in which the oxidation level of the sulfur is +VI. For example, a chlorosulfonate of the cell's active metal is formed.
  • the capacitance loss during charging and discharging depends on the solubility of the components in the electrolyte, the corresponding ranges are shown in the table.
  • the SO 2 consumption which is also variable according to the solubility of the reaction components.
  • the function of the cell may also be impaired or destroyed by the SO 2 consumption, because the charge transport in the electrolyte depends on the SO 2 concentration.
  • the cell should contain smaller overall quantities of disturbing oxides.
  • the cell therefore contains not more than 5 mMol, preferably not more than 2 mMol, especially not more than 1 mMol, particularly preferably not more than 0.5 mMol, and most preferably not more than 0.1 mMol of disturbing oxides per Ah theoretical capacitance of the cell.
  • This figure shows the O 2 ⁇ concentration in ppm, as determined by the Karl Fischer method, plotted against the time in days for three experiments, namely with the pure electrolyte (circles), the electrolyte with trimetal oxide (squares), and the electrolyte with graphite (triangles).
  • FIG. 2 This relates to electrochemical measurements with a cell having a three electrode configuration.
  • the figure plots the electrical voltage U in Volts against the time t in hours for the first charge of two different negative graphite electrodes.
  • For the first electrode commercial graphite without further treatment was used.
  • the second electrode was treated for 90 hours at 1000° C. in a kiln containing an argon protective gas, in order to remove the disturbing oxides.
  • the cell was charged with both electrodes at a constant current of 11 mA.
  • the resulting voltage-time curves are shown with A for the untreated electrode, and B for the pretreated electrode.
  • covering layers form on the graphite, specifically a covering layer of lithium dithionite, which is advantageous for the function of the cell, and an undesirable covering layer of lithium thiosulfate, which is formed because of the presence of disturbing oxides.
  • FIG. 2 shows that this voltage value was reached after 0.2 hours for the treated electrode and after 0.3 hours for the untreated electrode. Since the current flow was constant at 11 mA, it was possible to calculate a consumed charge quantity of 2.2 mAh for the pretreated, essentially oxide-free electrode, and 3.3 mAh for the untreated electrode. This shows that normal graphite contains relatively large quantities of disturbing oxides, which react when the cell is charged for the first time.
  • the disturbing oxide content in lithium cobalt oxide is extremely high. Although the values for the other electrode materials are approximately an order of magnitude lower, even these values are so high that the function of the cell would be severely impaired if the materials were used without prior treatment.
  • FIG. 3 shows results of measurements performed using Fourier Transformation Infrared (FTIR) spectroscopy.
  • FTIR Fourier Transformation Infrared
  • the figure shows the FTIR spectrum of an electrolyte with composition LiAlCl 4 ⁇ 1.5 SO 2 , which was taken from a cell after about 550 charging and discharging cycles (solid line A) compared with the same SO 2 electrolyte before it had been cycled (thin line B with crosses).
  • Absorbance a was plotted in arbitrary units against the wave number k in cm ⁇ 1 .
  • the spectrum shows typical maxima for the chlorosulfonate at about 1218 cm ⁇ 1 and 1070 cm ⁇ 1 .
  • the pronounced peak at about 1160 cm ⁇ 1 may be attributed to the sulfur dioxide in the electrolyte solution.
  • the formation of chlorosulfonate as a result of the cycling is evident.
  • FIG. 4 shows a measurement corresponding to FIG. 3 for the SO 2 electrolyte of a cycled cell (plot A as in FIG. 3 ) and for 3 calibration solutions that contained one percent by weight of chlorosulfonate (plot a), 3% chlorosulfonate (plot b), and 10% by weight chlorosulfonate (plot c).
  • the disturbing oxide content of the material of the positive electrode may be reduced by heating to elevated temperatures, wherein both the entire electrode (active material and current collector) and the active material alone may be subjected to the heat treatment.
  • a high temperature is advantageous but it must not be so high that fresh disturbing oxides are created (particularly due to reactions of a binding agent present in the electrode material).
  • carbon formed by the reduction of the binding agent in turn reduces the lithium metal oxide to a metal oxide, with the production of lithium oxide and carbon dioxide:
  • Heat treatment can also be applied to reduce the disturbing oxides content of the negative electrode to a value below the critical limit.
  • the graphite material or the entire electrode, including the current collector is heated to above 1000° C. in an inert gas atmosphere.
  • the resulting material is practically free from oxides, and has a consistency that is completely different to that of normal graphite. It flows like a liquid. Therefore, a special process is required in order to manufacture the negative electrode from oxide-free graphite.
  • another carbon material may be added (for example graphite that has been heated to 500° C., in a 15% concentration). Such an addition is sufficient to modify the flow behavior of the largely oxide-free graphite to such an extent that an electrode may be produced.
  • LiCl lithium chloride
  • the option exists to coat a graphite electrode (or the active mass thereof) with a thin layer of an inert ceramic material that is permeable to the ions of the conductive salt, particularly (Al 2 O 3 ). In this case too, it may be determined experimentally whether the oxide has been blocked sufficiently to prevent it from reacting with the sulfur dioxide, reducing the sulfur dioxide, and is no longer a disturbing oxide.
  • FIG. 5 shows the behavior of two cells with different disturbing oxide contents.
  • the discharge capacitance C (shown as a percentage of the initial capacitance) is plotted against cycle number N.
  • Curve A shows the cycle behavior of a cell containing about 0.25 mMol of oxygen in disturbing oxides on the positive electrode, about 0.25 mMol oxygen in disturbing oxides in the electrolyte, and about 1.1 mMol of oxygen in disturbing oxides on the negative electrode. Accordingly, the total content of oxygen in disturbing oxides was 1.6 mMol (per Ah theoretical capacitance of the cell in each case).
  • Curve B describes the cycle behavior of a cell with about 12 mMol oxygen contained in disturbing oxides per Ah theoretical capacitance of the cell.
  • the cell with fewer disturbing oxides still has a usable capacitance of about 50% after a thousand cycles, whereas the capacitance of the cell with the higher disturbing oxide content drops to very low levels even after fewer than a hundred cycles.
  • the cell with the lower disturbing oxide content had a capacitance of 1125 mAh after the lithium dithionite covering layer was formed. After 1000 cycles, it had a capacitance of approximately 414 mAh, capacitance loss was thus in the order of 709 mAh. With due allowance for measurement accuracy, this value corresponds well to the capacitance loss that may be calculated on the basis of the considerations outlined above.
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PL2534719T3 (pl) 2017-05-31
US20140113182A1 (en) 2014-04-24
KR20180114256A (ko) 2018-10-17
RU2569328C2 (ru) 2015-11-20
ES2617354T3 (es) 2017-06-16
KR20190128089A (ko) 2019-11-14
US9263745B2 (en) 2016-02-16
US10892487B2 (en) 2021-01-12
CN102742049A (zh) 2012-10-17
JP2013519968A (ja) 2013-05-30
CN102742062A (zh) 2012-10-17
EP3611788B1 (de) 2021-05-12
EP2360772A1 (de) 2011-08-24
JP5901539B2 (ja) 2016-04-13
EP3208869A1 (de) 2017-08-23
BR112012020118A8 (pt) 2018-01-02
EP2534725A1 (de) 2012-12-19
RU2012137863A (ru) 2014-03-20
EP3208869B1 (de) 2019-10-09
CN102742062B (zh) 2015-09-16
KR20130006614A (ko) 2013-01-17
EP3611788A1 (de) 2020-02-19
HK1173854A1 (zh) 2013-05-24
EP2534719B1 (de) 2017-01-25
BR112012020118A2 (pt) 2016-06-07
WO2011098233A3 (de) 2011-10-27
EP2534719A2 (de) 2012-12-19
AU2011214615B2 (en) 2015-05-21
KR101909084B1 (ko) 2018-10-17
EP2534725B1 (de) 2015-04-08
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