Two-Part Reference Electrode

Abstract

A two-part reference electrode for measuring impedance in a lithium-ion cell includes a first part (electrode Ref.sub.1) and a second part (electrode Ref.sub.2), each of which includes a metallic conductor. The first part and the second part are attached to a substrate separately from each other, and have a substantially constant spacing. The separator of the lithium-ion cell can act as a substrate. The electrode can be used for determining temperature and for detecting degradation of the electrode or electrolyte by way of impedance measurement. The electrode can also be used as a reference electrode for measuring half-cell potentials.

Claims

1.-17. (canceled)

18. A two-part reference electrode comprising: a first subelectrode comprising a first electrical conductor; and a second subelectrode comprising a second electrical conductor, wherein the subelectrodes are arranged electrically separately from one another on a substrate and have an essentially constant spacing.

19. The two-part reference electrode according to claim 18, wherein the spacing between the subelectrodes is between 10 μm and 1 mm.

20. The two-part reference electrode according to claim 18, wherein: the subelectrodes are arranged opposite to one another, each of the subelectrodes has an essentially comb-like shape, and teeth of a comb of the first subelectrode intermesh with teeth of a comb of the second subelectrode, such that the teeth of the comb of the first electrode are separated from the teeth of the comb of the second electrode by the spacing.

21. The two-part reference electrode according to claim 20, wherein each of the teeth has an essentially rectangular shape, and a tip of a tooth corresponds to a short side of the essentially rectangular shape.

22. The two-part reference electrode according to claim 21, wherein a width of the short side is between 10 μm and 1 mm.

23. The two-part reference electrode according to claim 18, wherein each of the subelectrodes is made of a metallic conductor.

24. The two-part reference electrode according to claim 23, wherein the metallic conductor is nickel, copper, silver, or gold.

25. The two-part reference electrode according to claim 18, wherein each of the subelectrodes has a layer thickness between 10 nm and 5 μm.

26. The two-part reference electrode according to claim 18, wherein the substrate is a porous separator film for a lithium ion cell.

27. The two-part reference electrode according to claim 26, wherein the subelectrodes are embedded between a separator substrate film and a separator covering film.

28. The two-part reference electrode according to claim 18, wherein the two-part reference electrode is configured as non-blocking electrode which allows charge exchange between the subelectrodes and surroundings of the two-part reference electrode.

29. The two-part reference electrode according to claim 18, wherein the two-part reference electrode configured as blocking electrode so that charge exchange between the subelectrodes and surroundings of the two-part reference electrode is blocked.

30. A separator film for a lithium ion cell, wherein the two-part reference electrode according to claim 18 is applied to the separator film.

31. A method for measuring an impedance of a lithium ion cell, the method comprising: applying an excitation signal between subelectrodes of a two-part reference electrode, wherein the two-part reference electrode comprises a first subelectrode comprising a first electrical conductor and a second subelectrode comprising a second electrical conductor, and the subelectrodes are arranged electrically separately from one another on a substrate and have an essentially constant spacing; and detecting a response signal.

32. The method according to claim 31, further comprising using the two-part reference electrode to measure a half-cell voltage relative to at least one of an anode or a cathode of the lithium ion cell.

33. The method according to claim 31, further comprising: determining a temperature of the lithium ion cell, and using a result of the impedance measurement to perform at least one of the following: (i) temperature determination; (ii) detection of covering layers or lithium plating; and (iii) determination of Li ion concentration in an electrolyte.

34. A method for measuring an impedance of a lithium ion cell comprising an anode, a cathode, a separator, an electrolyte, and a two-part reference electrode, wherein the two-part reference electrode comprises a first subelectrode comprising a first electrical conductor and a second subelectrode comprising a second electrical conductor, and the subelectrodes are arranged electrically separately from one another on a substrate and have an essentially constant spacing, the method comprising: applying an excitation signal I(t) between the subelectrodes of the two-part reference electrode; measuring a response signal U(t) between the subelectrodes of the two-part reference electrode; and determining the impedance as Z=U(t)/I(t).

35. A lithium ion cell comprising: an anode; a cathode; a separator; an electrolyte; and one or more two-part reference electrodes according to claim 18.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG. 1 schematically shows an embodiment of the reference electrode of the invention in which the two subelectrodes Ref.sub.1 and Ref.sub.2 each have an essentially comb-like shape. The teeth of the combs are intermeshed, with the spacing between the teeth of one comb and of the other comb being d.sub.1.

[0024] FIG. 2 schematically shows a further embodiment in which the teeth are widened to the width d.sub.2 and have an essentially rectangular shape.

[0025] FIG. 3 schematically shows an embodiment in which the reference electrode is embedded between two layers of porous separator film.

[0026] FIG. 4 schematically shows a further embodiment in which the reference electrode has been applied to one side of the separator as substrate. To provide electrical insulation from the anode, the latter is coated with a lithium ion-conducting ceramic.

[0027] FIG. 5 is a sketch of the measurement arrangement for measuring the impedance between the subelectrodes Ref.sub.1 and Ref.sub.2 and optionally for measuring the half-cell potentials U.sub.1 and U.sub.2 using the reference electrode as reference electrode.

[0028] FIG. 6 shows a simplified equivalent circuit diagram for use of the electrode according to an embodiment of the invention. The ratio of R.sub.1 and R.sub.2 can, for example, be set via the electrode spacing and the electrode area of the subelectrodes Ref.sub.1 and Ref.sub.2 (or d.sub.1 and d.sub.2 in the case of the embodiment of FIG. 2).

[0029] FIG. 7 schematically illustrates the detection of lithium plating with the aid of the reference electrode.

DETAILED DESCRIPTION OF THE DRAWINGS

[0030] The structure of the reference electrode according to embodiments of the invention, its mode of operation, its use in a lithium ion cell and the associated method for measuring the impedance are described in detail below.

Subelectrodes Ref.sub.1 and Ref.sub.2

[0031] The reference electrode of embodiments of the invention comprises two subelectrodes Ref.sub.1 and Ref.sub.2 which each comprise an electrical conductor and are arranged electrically separately from one another at an essentially constant spacing d.sub.1 on a substrate. After introduction into the cell, an impedance arises between Ref.sub.1 and Ref.sub.2 as a result of contact with the electrolyte, and this impedance can be measured.

[0032] The material of the electrical conductor is not subject to any specific restrictions, as long as it is chemically and electrochemically inert under the operating conditions. Possibilities are, for example, metallic conductors, semiconductors, which can optionally be doped, graphite or conductive polymers. Metallic conductors are preferred, in particular nickel, copper, silver, gold, platinum metals or alloys of these, and gold is more preferred in respect of chemical resistance and low layer thickness.

[0033] The two subelectrodes Ref.sub.1 and Ref.sub.2 are arranged at an essentially constant spacing d.sub.1. This means that the spacing of the subelectrodes is constant over the major part of their length, typically 70% or more, preferably 80% or more, in particular 90% or more. The spacing d.sub.1 is generally from 10 μm to 1 mm, preferably from 20 μm to 500 μm, in particular from 50 μm to 200 μm.

[0034] The subelectrodes can, for example, be configured as parallel conductor tracks, wires or strip conductors at a spacing d.sub.1, which can in turn be arranged in a zig-zag pattern, rectangular wave pattern or meandering pattern on the substrate.

[0035] In a preferred embodiment, the subelectrodes each have an essentially comb-like structure, i.e. they comprise a shaft section and a plurality of tooth sections projecting therefrom (hereinafter referred to as “shaft” and “teeth” in the interests of simplicity). The angle at which the teeth project is essentially the same for all teeth of both combs and is preferably a right angle. The two comb-like subelectrodes are arranged parallel to one another, so that the teeth of one comb mesh with those of the other and the spacing is in each case d.sub.1. FIG. 1 illustrates this embodiment.

[0036] The spacing of the comb shafts from one another is ultimately limited by the electrode geometry of the cell and is, for example, from 100 μm to 5 cm, preferably from 1 mm to 2 cm, in particular from 5 mm to 1 cm. In the case of teeth arranged at a right angle, this spacing is approximately the sum of d.sub.1 and the length of the teeth.

[0037] For trouble-free integrability into the cell, the thickness of the two subelectrodes is preferably 10 μm or less, more preferably 1 μm or less, particularly preferably 500 nm or less. In a preferred embodiment, the layer thickness is from 10 to 100 nm, which can be realized by, for example, vapor deposition processes (e.g. sputtering of a 20 nm gold film).

[0038] The width can be the same as the thickness, or the two subelectrodes can be broadened in order to increase the surface area of the reference electrode and thus reduce the resistance relative to the electrolyte.

[0039] Accordingly, the two subelectrodes can, for example, have an essentially round or square cross section and, for instance, be configured in the form of thin wires, they can be strip-like with a rectangular cross section or they can be made up of flat sections which are joined by wire-like or strip-like sections.

[0040] A preferred embodiment is shown in FIG. 2. It is based on the embodiment shown in FIG. 1 with two intermeshed, comb-like subelectrodes, but the teeth are broadened to form rectangles. The width of the rectangles d.sub.2 is proportional to the area and can be in the same order of magnitude as the spacing d.sub.1.

[0041] The ratio d.sub.1/d.sub.2 is preferably in the range from 20:1 to 1:20, more preferably from 10:1 to 1:10, in particular from 5:1 to 1:5. The ratio d.sub.1/d.sub.2 is the ratio of spacing and area of the two subelectrodes. Selection of this ratio makes it possible to set the relative contributions of the impedances arising between Ref.sub.1 and Ref.sub.2, as described in detail below.

Application to the Substrate

[0042] The two subelectrodes Ref.sub.1 and Ref.sub.2 have been applied to a substrate. The substrate can generally be a polymer film, for example composed of PET or polyolefin.

[0043] In one possible embodiment, the two subelectrodes are applied to a strip of film and the strip of film is introduced into the cell in such a way that the two subelectrodes face the separator in order to avoid electrical contact with the working electrode.

[0044] The strip of film is in this case preferably very narrow and thin in order to keep local disturbance as small as possible. Preferred dimensions for the length and width of the section introduced are, for example, from 2 mm to 2 cm, preferably from 5 mm to 1 cm. The thickness can preferably be from 1 to 20 μm, preferably from 5 to 10 μm.

[0045] However, the use of a nonporous substrate such as a strip of film will always lead to a local change in the current density of the cell during operation, so that Li plating occurs at the margins of the reference electrode at an early juncture during charging of the cell. The reference electrode can therefore also be used as an early indicator for the detection of Li plating in this embodiment, in order possibly to allow the charging current to be reduced before plating occurs at further places in the cell. The suitability of the reference electrode for temperature determination via the conductivity of the electrolyte is not influenced, or influenced only negligibly, by this local disturbance occurring at the margins.

[0046] In a further embodiment, the separator of the cell can itself function as substrate. This embodiment is preferred since no additional layer of film is introduced and consequently the thickness of the cell is not increased and since the reference electrode can in principle extend over the entire area of the separator.

[0047] In addition, it is made possible in a simple way for a plurality of reference electrodes to be introduced into the cell by, for example, a plurality of spatially separated pairs of subelectrodes Ref.sub.1/Ref.sub.2 being applied simultaneously to different regions of the separator film. This makes it possible to achieve, for example, spatial resolution of the impedance measurement, or the reference electrodes can have a different geometry (e.g. different ratios of spacing and area) and thus be optimized for examining different phenomena or elements of the cell.

[0048] The separator is typically a porous polymer film, usually composed of polyethylene (PE) or polypropylene (PP). The separator can also be a shutdown separator which comprises a laminate of PP/PE/PP. PE has a lower melting point that PP, so that the PE layer can melt in the case of an abnormal temperature rise and close the pores of the PP layers (“shutdown effect”). In addition, the separator can also have a coating composed of ceramic material.

[0049] The subelectrodes Ref.sub.1 and Ref.sub.2 can have been applied to the surface of the separator and have been provided with a covering layer which is permeable to lithium ions in order to effect electrical insulation. The covering layer can be a second layer of the separator film or be a coating comprising an electrically insulating, lithium ion-conducting material. In particular, the subelectrodes can be embedded between the layers when using a multilayer separator or a separator coated with ceramic material. FIG. 3 illustrates such an arrangement.

[0050] As an alternative, a covering layer on the reference electrode can also be dispensed with. In this case, however, an appropriate covering layer, for example a coating comprising a ceramic lithium ion conductor, is to be provided on the working electrode of the cell adjoining the subelectrodes Ref.sub.1 and Ref.sub.2 in order to effect electrical insulation. This embodiment is shown in FIG. 4. The surface of the reference electrode can also be provided with a coating which is impermeable to Li ions.

[0051] A configuration in which charge exchange with the electrode is blocked is referred to below as blocking electrode and a configuration in which charge exchange is possible is referred to below as non-blocking electrode. In the case of metal electrodes which are in contact with the electrolyte, the ability for lithium ion exchange to occur depends on the applied potential which has to be low enough to make lithium plating or alloy formation possible. Thus, such an electrode can be operated either as blocking electrode or as non-blocking electrode as a function of the potential.

[0052] In the case of the blocking electrode, the subelectrodes lose their ability to be used as reference electrode since the electrochemical potential can no longer be determined. Measurement of the impedance between the two subelectrodes is nevertheless possible, with the impedance at the interfaces between subelectrode and electrolyte being purely capacitive.

[0053] The process for application to the substrate is not subject to any specific restrictions and can depend on the electrode material and the desired geometry. Preference is given to vapor deposition processes such as PVD, CVD, sputtering or the like. The desired geometry can be realized by use of masking techniques. As an alternative, ink jet printing processes, for example, are also possible.

[0054] The places of contact of the reference electrode can be provided, for example, in the form of widened contact pads which are then conducted out of the cell via, for example, film conductors or thin gold wires. As an alternative, the substrate can provide an overhang on which the places of contact are provided and which is conducted out of the cell. For this purpose, a sealable opening through which the conductors or strips of film are conducted can be provided in the housing of the cell, or a place of contact to which the places of contact of the reference electrode are joined in the interior of the housing and which provides appropriate connections outside on the housing can be provided.

Impedance Measurement

[0055] The reference electrode according to embodiments of the invention can be used in combination with any types of lithium ion cells, especially in cells having a liquid electrolyte of the roll type or stack type.

[0056] It is intended first and foremost for temperature determination, for detection of undesirable electrode phenomena such as Li plating and for determination of the Li ion concentration by way of impedance measurement. In addition, it can optionally also be used, for example between two impedance measurements, as reference electrode for measuring the half-cell potential relative to anode or cathode.

[0057] For use for impedance measurement, an excitation signal is applied between the two subelectrodes Ref.sub.1 and Ref.sub.2 and the response signal is measured. The excitation signal can be, for example, an alternating current signal I(t), while the potential U(t) is measured as response signal. The impedance is then calculated as Z=U(t)/I(t). The measurement arrangement is illustrated in FIG. 5.

[0058] Compared to conventional impedance measurement by application of the excitation signal to the working electrodes, the reference electrode according to embodiments of the invention has the advantage that a precise impedance measurement can be carried out with a smaller excitation current. This leads to improved accuracy in the temperature determination via the impedance and to improved local resolution. In addition, ageing phenomena of the electrolyte and/or the working electrode, in particular Li plating on the anode, for example, can be detected in a targeted manner using the electrode of embodiments of the invention by suitable choice of the geometry.

[0059] FIG. 6 shows a simplified circuit diagram of the components which contribute to the impedance between Ref.sub.1 and Ref.sub.2. The interfaces between electrode and electrolyte can in the case of configuration as blocking electrode be modelled as purely capacitive resistances and the electrolyte or the active layer of the working electrode can be modelled as ohmic resistances, as shown in the figure.

[0060] At relatively high frequencies, the capacitive contributions become negligible, so that the impedance is determined essentially by the parallel ohmic resistances R.sub.1 and R.sub.2. R.sub.1 is the resistance of the direct electrical connection from Ref.sub.1 to Ref.sub.2 through the electrolyte, and R.sub.2 is the connection of Ref.sub.1 to the working electrode and from this back to Ref.sub.2. In other words, R.sub.1 essentially represents the electrolyte resistance between Ref.sub.1 and Ref.sub.2 and R.sub.2 represents essentially the resistance of the active layer of the working electrode.

[0061] What has been said above in respect of blocking electrodes also applies in an analogous way to non-blocking electrodes at high frequencies. Here, the interfaces are no longer purely capacitive, as shown in FIG. 6, but are instead represented as parallel connection of capacitive resistance and ohmic resistance, which reflects the charge exchange. At low frequencies, both parts are important for the impedance contribution of the electrode interface. At high frequencies, on the other hand, the capacitive part turns to zero while the ohmic part remains finite, so that the impedance of the parallel connection again becomes negligible. In this case, the total impedance is thus likewise determined by the two parallel resistances R.sub.1 and R.sub.2.

[0062] R.sub.1 here depends both on the electrode area and on the spacing d.sub.1 which indicates the distance travelled by the charge carriers in the electrolyte. R.sub.2, on the other hand, is determined mainly by the electrical conduction through the active material layer in the thickness direction, while conduction occurs along the surface via the metallic power outlet lead, the resistance of which is negligible. R.sub.2 thus depends to a good approximation solely on the electrode area.

[0063] The relative contribution of R.sub.1 and R.sub.2 to the impedance can be set by appropriate choice of the geometry, in particular the ratio of spacing d.sub.1 and area of the reference electrode, e.g. by choice of the d.sub.1/d.sub.2 ratio in the case of the embodiment shown in FIG. 2. The electrolyte conductivity and the constitution of the working electrode can in this way be examined in a targeted manner in order to be able to arrive at a differentiated ageing diagnosis. Furthermore, it is also possible to use a plurality of reference electrodes according to embodiments of the invention having different spacing/area ratios (or d.sub.1/d.sub.2 ratios) which are, for example, applied together to the separator in order to be able to examine the two properties independently. When using a plurality of reference electrodes, these can also be actuated in succession, for example by being joined alternately to the excitation device and the measurement device in a multiplex process.

[0064] The excitation frequencies depend on the properties to be diagnosed and are generally in the range from 10 Hz to 20 kHz, preferably from 50 Hz to 10 kHz. To measure the electrolyte conductivity and detect any lithium plating on the anode, preference is given, as indicated above, to high frequencies of, for example, from 500 Hz to 20 kHz, more preferably from 1 kHz to 10 kHz, so that the impedance is determined essentially by the resistances R.sub.1 and R.sub.2. Should, on the other hand, properties related to charge exchange and the capacitive double layer on the electrodes be determined, for instance for studying the dielectric properties of the electrolyte and thus also the formation of possible covering layers or a change in the ion concentrations, use is made of low frequencies, for example in the range from 10 Hz to 1 kHz, preferably from 50 Hz to 500 Hz.

[0065] The signal level of the excitation signal is typically in the range from 1 to 50 mV. Preference is given to using levels of from 5 to 20 mV, for example about 10 mV, in order firstly to maintain the linearity of the system and secondly to keep the outlay for the measurement small. Relatively high amplitudes make better resolution possible at the expense of possible nonlinearity, whereas relatively low amplitudes make determination of the measured values more difficult.

[0066] In addition to the alternating current signal, a polarization potential can be applied between the two subelectrodes. In this way, it is possible to characterize the charge carrier double layer on the surfaces, which is dependent on the electrolyte composition, ion concentration and thus also on ageing.

Temperature Determination

[0067] The reference electrode of an embodiment of the invention can be used for determining temperature by way of impedance measurement using the known relationship between temperature and impedance T(Z). T(Z) is typically recorded in the form of look-up data and/or a calculation model in the battery management system, possibly as a function of further parameters such as SOC or ageing state.

[0068] The determination of T(Z) is known in principle. Thus, T(Z) can be determined, for example, by acquisition of calibration data in which the cell is brought to a particular temperature and a particular SOC and the impedance is measured. As an alternative or in combination therewith, T(Z) can also be calculated, for instance with the aid of an impedance model in combination with a known temperature dependence of the constituents of the model. For the temperature dependence of the impedance contributions which depend on the kinetics of the electrode processes, it is possible to use, for example, an Arrhenius relationship, and for the electrolyte conductivity it is possible to use the known temperature dependence of ion mobility as a basis.

Detection of Lithium Plating

[0069] In addition, the reference electrode of an embodiment of the invention is also particularly suitable for detecting undesirable electrode processes, such as the formation of defects in the interfacial layer between anode and electrolyte (SEI) or the deposition of metallic lithium (Li plating), which are associated with a change in the impedance.

[0070] FIG. 7 illustrates this for the case of lithium plating, which is shown by a sharp drop in the impedance. This is caused by formation of a bridge of metallic Li between anode and one of the two subelectrodes Ref.sub.1 or Ref.sub.2, or between the two subelectrodes, as shown in the figure, which leads to a sharp decrease in the ohmic resistance or in the extreme case to a short circuit between the two subelectrodes.

[0071] In the case of lithium plating, the reference electrode additionally acts as defined point of disturbance, i.e. the deposition preferentially occurs firstly in the vicinity of the reference electrode, and/or dendrites of Li grow in the direction of the reference electrode, due to the electric field between reference electrode and anode, and the probability of deposition in other places is decreased. The reference electrode is therefore particularly suitable for early recognition of such lithium plating.

Determination of the Lithium Ion Concentration

[0072] The lithium ion concentration can be determined by examination of the dielectric properties at the interface of the subelectrodes. As indicated above, relatively low excitation frequencies at which the capacitive resistance does not vanish but is instead frequency-dependent with −1/ωC, where C is the capacitance of the double layer, are typically used for this purpose. In addition, a variable direct potential signal (bias) superposed on the alternating signal can be applied to the electrode. Here, a bias potential of, for example, 200 mV is applied between the two electrodes, the alternating current impedance is determined and the alternating current impedance is subsequently determined again at a different bias potential of, for example, 400 mV. Since the magnitude of the charge carrier double layer depends on the polymerization potential and the ion concentration, the prevailing ion concentration can be determined from the dependence now determined on the polarization potential.

Use as Reference Electrode for Potential Measurement

[0073] In addition, the reference electrode of an embodiment of the invention can optionally also be used, for example between two impedance measurements, as reference electrode for measuring the half-cell potential relative to anode or cathode, as is likewise illustrated in FIG. 5. To provide a stable reference potential, a small amount of metallic lithium is firstly deposited on one or both subelectrodes (in-situ lithiation) so that the potential corresponds to that of Li/Li.sup.+. The potential relative to the working electrode is then measured. Since the measurement occurs to a good approximation without current, the reference potential remains constant.

[0074] As an alternative to deposition of metallic lithium, lithium alloys can also be formed, depending on the material of the reference electrode (e.g. in the case of aluminum or gold). These alloys typically have a step-like course which is dependent on the lithium concentration. In such a case, it is advantageous to actuate a very pronounced potential step, (i.e. a potential step which prevails over a wide lithium concentration range and changes comparatively sharply at the margins) with high capacitance in order to avoid changes in the reference potential due to spontaneous discharge. In addition, metallic lithium can also be deposited on the alloy formed. In the case of materials such as copper which do not form an alloy, metallic lithium has to be deposited in any case. Furthermore, the availability of two subelectrodes can advantageously be used to detect spontaneous discharge of a subelectrode and recharge it.