# Patent

## Title
Electrochemical energy store and method for determining the wear to an electrochemical energy store

## Abstract

A method for determining the wear to an electrochemical energy store and an electrochemical energy store allows for continuously determining the amounts of charge (qL) converted during charging cycles of the energy store and calculating a wear variable (Qv) which characterizes the wear as a function of the determined converted amount of charge (qL).

## Background
BACKGROUND
The invention relates to a method for determining the wear to an electrochemical energy store resulting from the loss of storage capacity, and to an energy store, in particular a starter battery for motor vehicles, having measurement means for determining the amounts of charge converted during the charging cycles of the energy store, and having computation means.
Energy stores, for example rechargeable electrochemical storage batteries, are subject to wear, in particular during discharging and charging. In addition to discharging and charging, there are also other operating conditions which speed up the wear to electrochemical energy stores. These include, for example, the total operating life in the case of a lead-acid rechargeable battery, that is to say the total time which has passed since it was brought into use, including the periods in which the rechargeable battery had no electrical load applied to it.
Furthermore, increased temperatures can increase the wear during periods without any electrical load being applied, and the wear caused by cyclic discharging and charging.
For the use of energy stores, it is desirable to determine the wear on the basis of the loss of storage capacity. However, the complexity of the processes that take place in the energy store represent a problem in this case, which can be described only with difficulty by using scientific methods.
By way of example, DE 195 40 827 C2 discloses an empirical method for determining the aging state of a battery, in which a battery-specific family of characteristics is predetermined for battery aging. A battery aging value is determined with the aid of the family of characteristics by recording instantaneous values of battery aging influencing variables for the battery that is being monitored.
DE 39 01 680 C3 discloses a method for monitoring the cold starting capability of a starter battery in which, when the internal combustion engine is running, the charging voltage is observed continuously and is monitored to determine whether it has exceeded or fallen below predetermined limit values. This makes it possible to identify a defect in the generator. Furthermore, the time profile of the voltage drop across the connecting terminals of the electrical starter is observed and evaluated during the starting process. However, in this case, it is not possible to make any statement about the available storage capacity of the energy store.
DE 38 08 559 C2 discloses a method for monitoring the power limit of a starter battery, in which an amount of charge balance is produced by adding up the amounts of charge which have flowed in and flowed out. The state of charge of the starter battery is assessed from this, in conjunction with the monitoring of a limiting terminal voltage and the temperature. It is not possible to make any statement about the remaining maximum storage capacity of the energy store in this case, either.
The object of the invention was thus to provide a method for determining the wear to an electrochemical energy store resulting from the loss of storage capacity, by means of which a wear variable can be calculated reliably and using simple means, as a measure of the loss of storage capacity.
SUMMARY OF THE INVENTION
An exemplary embodiment relates to a method for determining the wear to an electrochemical energy store. The method includes continuously determining the amounts of charge (qL) converted during charging cycles of the energy store. The method also includes calculating a wear variable (Qv) which characterizes the wear as a function of the determined converted amount of charge (qL).
Another exemplary embodiment relates to an energy store, in particular a starter battery for motor vehicles. The energy store includes measurement means for determining the amounts of charge (qL) converted during charging cycles of the energy store. The energy store also includes computation means designed to calculate a wear variable (Qv) which characterizes the loss of storage capacity as a function of the determined amount of charge (qL) converted.



BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be explained in more detail in the following text using the attached drawing, in which:
FIG. 1 shows an illustration of a model of an electrochemical energy store.



DETAILED DESCRIPTION OF THE PREFERRED AND EXEMPLARY EMBODIMENTS
According to an exemplary embodiment, the present invention provides a method for determining the wear to an electrochemical energy store that utilizes continuous determination of the amounts of charge converted during the charging cycles of the energy store and calculation of a wear variable which characterizes the loss of storage capacity as a function of the determined converted amount of charge.
Surprisingly, it has been found that the wear to an energy store can be determined easily and accurately by considering the amount of charge with which the energy store has been charged. This can be explained by the fact that the charging process governs the structural changes (which cause the wear to the energy store) in the electrochemical active materials and, furthermore, overcharging that affects wear is taken into account. In this case, it was recognized that the loss of storage capacity increases progressively as the amount of charge converted during the charging cycles increases, and that the discharging cycles have no significant influence on this loss.
The amounts of charge converted are preferably determined from the sum of the amounts of charge fed into the energy store, for example by continuous integration of the charging current which flows into the energy store, or by recording changes in the state of charge of the energy store.
It was also recognized that very small charge flows in the charging or discharging direction, which alternate, contribute only a small amount or nothing to the wear to the energy store. The amounts of charge converted, and which are included in the calculation of the wear variable, should thus be greater than a defined minimum amount of charge per charging cycle. Small contributions to the charge flow are thus ignored when determining the wear. The minimum amount of charge is preferably in the range from 0.1 to 1×10−6 times, and particularly preferably in the range from 0.01 to 0.001 times, the initial capacity of an equivalent new energy store.
By way of example, the wear variable may be determined in proportion to a wear function which comprises the sum of at least the terms a0, a1×qk and a2×ql, (f(q)=a0+a1×qk+a2×ql). The parameters a0, a1 and a2 are in this case constant. The variable q denotes the amounts of charge converted, the parameter k has values of less than or equal to unity, and the parameter l has values of greater than unity.
It is particularly advantageous for the wear function to be developed into a power series at a development point q0, which comprises a sum of at least the terms a1×(q−q0)k and a2×(q−q0)l and a constant a0. The parameters a1 and a2 are constant. The variable q once again denotes the amount of charge converted, and the parameter k has values of less than or equal to unity, and the parameter l has values of greater than unity.
The wear function can also be developed into a Taylor series at the development point q0, which comprises a sum of at least the constant value f(q0) of the wear function at the development point q0 and at least the terms f′(q0)×(q−q0) and (f′′(q0)/2)×(q−q0)2. The constant f′(q0) is the first derivative of the wear function at the development point q0, and f′′(q0) is the second derivative.
The wear variable is preferably determined in 15 proportion to the initial capacity of an equivalent new energy store, for example from the product of the wear function and the initial capacity. However, it may also be proportional to the capacity of an identical energy store at a different operating time.
By way of example, a wear function f(q)=0.0013×qL+4×10−5×qL2 has been found to be suitable for determining the wear for a lead-acid starter rechargeable battery, with the amount of charge qL being measured in units of the rated capacity of the lead-acid starter rechargeable battery.
It is particularly advantageous to determine a characteristic value for the present storage capacity of the energy store from the difference between the initial capacity of an equivalent new energy store and the wear variable. This characteristic value can be indicated for the present storage capacity, can be used for further calculations, or can be used as a control parameter.
In one development of the method according to the invention, the wear variable may also be linked to further state variables which describe the state of the energy store and are determined using conventional methods. State variables such as these may, f or example, be the total operating life of the energy store, the temperature influences, the state of charge, the readiness to produce power, etc.
Another exemplary embodiment relates to an energy store of this generic type by means of computation means which are designed to calculate a wear variable which characterizes the loss of storage capacity as a function of the determined amount of charge converted, using the method described above.
Rechargeable electrochemical energy stores are generally used in two different operating modes.
During pure charging/discharging, charging and discharging phases which are limited in time with respect to one another alternate. The charging phase is in this case generally continued until a defined state, preferably the fully charged state, is reached. This is often followed at a later time by a discharging phase, whose end is defined either by the end of the energy requirement or by exhaustion of the energy store.
When charging and discharging phases alternate, the phase lengths and the amounts of charge converted in the process may differ widely. Normally, the energy store never reaches either the fully charged state or the exhausted state.
Pure charging/discharging is typical, for example, for electrical vehicles such as fork-lift trucks, for flashlights and for portable electronic appliances such as laptops, mobile telephones and camcorders etc. Alternating operation occurs, in contrast, for the vehicle power supply system battery in motor vehicles or generally in so-called island modes, such as those which occur in other vehicles, such as ships, trains, aircraft and space vehicles, or in local power supply networks with battery backup which are supplied, for example, by fuel, solar power or wind power.
During pure charging/discharging, generally relatively large charge flows with respect to the storage capacity of the energy store follow one another alternately in the charging and discharging directions. During alternating operation, on the other hand, very small charge flows often occur in the charging or discharging direction before the mathematical sign of the current flowing through the energy store is reversed once again.
FIG. 1 shows a sketch of an energy store in which an amount of charge qL is fed in the charging cycle, and a discharge amount qE is drawn in a discharging cycle. When in a new state, the energy store has an initial capacity Qn for charge storage. During its life, the available storage capacity Qact decreases owing to wear. The wear variable Qv characterizes the loss of available storage capacity Qact.
It has now been found that the wear in the form of the loss of available storage capacity Qact continues as the amount of charge converted during charging increases, with the wear taking place progressively. The flow of the same amount of charge thus on the one hand leads to greater wear the greater the amount of charge which has already flowed through the energy store in total.
It has also been found that very small charge flows in the charging or discharging direction, which alternate, have scarcely any influence on the wear of the energy store. This is primarily due to the fact that very small charge flows lead only partially, or not at all, to electrochemical reactions in the electrochemical energy store and, instead, are borne at least partially by other processes, such as charge reversal of the Helmholtz double layer between a solid body and the electrolyte. The amount of charge qL, which is converted and is taken into account in order to determine the wear thus includes only those amounts of charge qL which, within a charging cycle, exceed a minimum amount of charge qmin in the range from 0.1 to 1×10−6 times the initial capacity Qn of an equivalent new energy store. The amount of charge qL, converted should preferably exceed a minimum amount of charge qmin in the range from 0.01 to 0.001 times the initial capacity Qn.
The amount of charge converted during one charging cycle is determined, for example, by integration of the measured, calculated or estimated current. Alternatively, the amount of charge qL converted can be determined by measurement, calculation or estimation of a change in the state of charge which, for example, may be derived from a measurement of the no-load voltage, or from some other voltage.
The wear variable Qv is then determined as a function f(qL) of the determined amount of charge qL converted.
The function may consist, for example, of the sum of at least the terms a0, a1×qk and q2×ql:

f(q)=a0+a1×qk+a2×ql.

In this case, a0, a1 and a2 are constant parameters. The parameter k is defined such that it assumes values of less than or equal to unity, and the parameter l is greater than unity.
In one particular refinement of the method, the wear function is defined as:

f(qL)=a1×qL+a2×qL2.

The coefficients a1=0.0013 and a2=4×10−5 have been found to be optimum values for a lead-acid starter rechargeable battery.
The wear function f(q) can also be developed into a power series at the development point q0, and consists at least of the following sum:

f(q)=a0+a1×(q−q0)k+a2×(q−q0)l.

In this case, a0, a1 and a2 are once again constant parameters, and the parameters k are defined for values of less than or equal to unity, and l for values of greater than unity.
The wear function f(q) may also be developed into a Taylor series at the development point q0, which has at least the following sum:

f(q)=f′(q0)×(q−q0)+(f′′(q0)/2)×(q−q0)2.

The wear variable Qv is then preferably calculated from the product of the wear function f(qL) and the initial capacity Qn.
The storage capacity Qact available at any given time is calculated from the difference between the initial capacity Qn and the wear variable Qv:

Qact=Qn−Qv=Qn(1−f(qL)).

Priority application DE 102 15 071.0 filed on Apr. 5, 2002, including the specification, drawing, claims, and abstract, is incorporated herein by reference in its entirety.
It is important to note that the construction and arrangement of the elements of the energy store as shown and described in the preferred and other exemplary embodiments is illustrative only. Although only a few embodiments of the present inventions have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible without materially departing from the novel teachings and advantages of the subject matter recited herein. It should be noted that the elements and/or assemblies of the system may be constructed from any of a wide variety of materials that provide sufficient strength or durability. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the preferred and other exemplary embodiments without departing from the scope of the present invention.

## Claims

1. A method for determining the wear to an electrochemical energy store, comprising:
continuously determining the amounts of charge (qL) converted during charging cycles of the energy store; and
calculating a wear variable (Qv) which characterizes the wear as a function of the determined converted amount of charge (qL);
wherein the determined converted amount of charge (qL) is greater than a defined minimum amount of charge (qmin) per charging cycle; and
wherein the minimum amount of charge (qmin) is in the range from 0.1 to 1×10−6 times an initial capacity (Qn) of an equivalent new energy store.

2. The method of claim 1 wherein determining the converted amount of charge (qL) utilizes a sum of the amounts of charge fed into the energy store.

3. The method of claim 1 wherein determining the amount of charge (qL) converted includes continuously integrating charging current (IL) which flows into the energy store.

4. The method of claim 1 wherein determining the amounts of charge (qL) converted includes detecting state of charge changes in the energy store.

5. The method of claim 1 wherein the amounts of charge (qL) are greater than a defined minimum amount of charge (qmin) per charging cycle.

6. The method of claim 1 wherein the minimum amount of charge (qmin) is in the range from 0.01 to 0.001 times the initial capacity (Qn) of the equivalent new energy store.

7. The method of claim 1 wherein the wear variable (Qv) is proportional to a wear function (f(q)), the wear function (f(q)) comprising the sum of at least the terms a0, a1×qk and a2×q1, where a0, a1 and a2 are constant parameters, q is the amount of charge converted and the parameter k is less than or equal to unity, and the parameter 1 is greater than unity.

8. The method of claim 1 wherein the wear variable (Qv) is proportional to a wear function (f(q)), the wear function (f(q)) being developed as a power series at a development point (q0) and comprising a sum of at least the terms a1×(q−q0)k and a2×(q−q0)1and a constant a0, where a1 and a2 are constant parameters, q is the amount of charge converted, and the parameter k is less than or equal to unity, and the parameter 1 is greater than unity.

9. The method of claim 1 wherein the wear variable (Qv) is developed proportionally to a wear function (f(q)) into a Taylor series at a development point (q0) comprising a sum of a constant value (f(q0)) of the wear function (f(q)) at the development point (q0) and at least the terms f′(q0)×(q−q0) and (f′′(q0)/2)×(q−q0) 2, where f′(q0) is the first derivative of the wear function (f(q)) at the development point (q0) and f′(q0) is the second derivative of the wear function (f(q)) at the development point (q0).

10. The method of claim 1 wherein the wear variable (Qv) is proportional to an initial capacity (Qn) of an equivalent new energy store.

11. The method of claim 1 wherein calculating the wear variable (Qv) utilizes the product of a wear function (f(q)) and an initial capacity (Qn) of an equivalent new energy store.

12. The method of claim 1 further comprising determining a characteristic value for a present storage capacity (Qact) of the energy store from the difference between an initial capacity (Qn) of an equivalent new energy store and the wear variable (Qv).

13. The method of claim 1 wherein the wear variable (Qv) is linked to further state variables which describe the state of the energy store.