JP2022056999A - Method for measuring battery performance instantly - Google Patents
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- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/367—Software therefor, e.g. for battery testing using modelling or look-up tables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
- G01R31/387—Determining ampere-hour charge capacity or SoC
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/02—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries for charging batteries from ac mains by converters
- H02J7/04—Regulation of charging current or voltage
- H02J7/06—Regulation of charging current or voltage using discharge tubes or semiconductor devices
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Abstract
Description
本発明は、電池性能の指標である容量と、この容量に対する現在の充電比率SOC(蓄電比率)を、短時間で(具体的には1秒程度で)検知可能とする電池性能の瞬時計測方法に関する。 The present invention is a method for instantaneously measuring battery performance, which enables detection of a capacity, which is an index of battery performance, and a current charge ratio SOC (storage ratio) with respect to this capacity in a short time (specifically, in about 1 second). Regarding.
従来、電池性能を検知するためには、満充電まで充電し、その後、完全放電までの積算電気量を計量し、その結果の数値を基準に、電池の良し悪しを評価する性能認識をしていたが、これらの一連の作業には数時間要している。 Conventionally, in order to detect battery performance, the battery is charged until it is fully charged, then the integrated amount of electricity until it is completely discharged is measured, and the performance recognition is performed to evaluate the quality of the battery based on the resulting numerical value. However, these series of operations take several hours.
しかし、電池を使う立場で考えるに、性能認識は、電池を使用する機器の製造工程、及び搭載する電池の安全性・信頼性を担保する検査工程においても不可欠であり、次工程への重要な事前確認事項である。この性能認識を短時間で可能とすることは、物理的にも経済的にも極めて重要な課題であった。 However, from the standpoint of using batteries, performance recognition is indispensable in the manufacturing process of equipment that uses batteries and in the inspection process that ensures the safety and reliability of the installed batteries, and is important for the next process. This is a matter to be confirmed in advance. Making this performance recognition possible in a short time has been an extremely important issue both physically and economically.
特許文献1には、動的内部抵抗が電池性能指標となることから基準の電池に対する比率から性能比率を算出する交流インピーダンス法が開示されている。また、特許文献2等には、電解質と電極の組み合わせに応じた複素応答特性を観測する手法が開示されている。このように、過去、幾多の手法が試みられているが、いずれも、実用上あるいは実装上、様々な難点があり、特殊用途の使用にとどまっている。
Since the dynamic internal resistance serves as a battery performance index,
本発明の目的は、電池の性能を短時間で検知することを可能とする電池性能の瞬時計測方法を提供することである。 An object of the present invention is to provide a method for instantaneously measuring battery performance, which makes it possible to detect battery performance in a short time.
本発明に係る電池性能の瞬時計測方法は、電池の開放電圧である起電力Vemfを計測する工程と、前記電池の種類に基づいて、該電池のパラメータであるVs及び移動度αを求める工程と、数1の式に基づいて、充電比率SOCに対応するC*
rを算出する工程と、数2の式に基づいて、SOC依存関数値を算出する工程と、を備えることを特徴とする。
また、本発明に係る電池性能の瞬時計測方法において、前記起電力Vemfに対し過電圧ΔV1を加算して前記電池に印加したときに流れる電流I1を算出する工程と、前記起電力Vemfに対し過電圧ΔV2を加算して前記電池に印加したときに流れる電流I2を算出する工程と、数3の式に基づいて、真の過電圧δ1を求める工程と、数4の式に基づいて、真の過電圧δ2を求める工程と、を備えることが好ましい。
また、本発明に係る電池性能の瞬時計測方法において、前記真の過電圧δ1及び前記真の過電圧δ2を計測し、電池の動作状態が正常であるか異常であるかを判定する工程を備えることが好ましい。 Further, the method for instantaneously measuring battery performance according to the present invention includes a step of measuring the true overvoltage δ 1 and the true overvoltage δ 2 and determining whether the operating state of the battery is normal or abnormal. Is preferable.
また、本発明に係る電池性能の瞬時計測方法において、数5の式に基づいて、電池性能係数K00を算出する工程を備えることが好ましい。
また、本発明に係る電池性能の瞬時計測方法において、前記真の過電圧δ1及び前記真の過電圧δ2に対し、前記電池の内部では電極反応を介して電流として応答し、該応答時間は電池状態によって異なり、前記応答時間を組み入れて電池性能係数K00を算出する工程を備えることが好ましい。 Further, in the instantaneous measurement method of battery performance according to the present invention, the true overvoltage δ 1 and the true overvoltage δ 2 are responded to as a current through an electrode reaction inside the battery, and the response time is the battery. It depends on the state, and it is preferable to include a step of calculating the battery performance coefficient K00 by incorporating the response time.
本発明によれば、電池の性能を短時間で検知することが出来る。 According to the present invention, the performance of the battery can be detected in a short time.
以下に、本発明に係る実施の形態について添付図面を参照しながら詳細に説明する。以下では、全ての図面において同様の要素には同一の符号を付し、重複する説明を省略する。また、本文中の説明においては、必要に応じそれ以前に述べた符号を用いるものとする。 Hereinafter, embodiments according to the present invention will be described in detail with reference to the accompanying drawings. In the following, similar elements are designated by the same reference numerals in all drawings, and duplicate description will be omitted. In addition, in the explanation in the text, the reference numerals described earlier shall be used as necessary.
図1は、本発明に係る実施形態において、電池内部の電気等価回路図である。記号は、以下を意味する。V:電極端子間電圧、I:電流、η* eq:平衡電圧(=起電力Vemf),δ:過電圧、ΔVD:電極反応抵抗に伴う電位差,ΔVC:電解質中のカチオンの拡散・泳動に伴う電位差、R,C:等価抵抗、キャパシター。 FIG. 1 is an electrical equivalent circuit diagram inside a battery according to an embodiment of the present invention. The symbols mean the following: V: Voltage between electrode terminals, I: Current, η * eq : Equilibrium voltage (= electromotive force Vemf ), δ: Overvoltage, ΔV D : Potential difference due to electrode reaction resistance, ΔVC : Diffusion / migration of cations in electrolyte Potential difference associated with, R, C: equivalent resistance, capacitor.
図2は、本発明に係る実施形態において、過電圧-電流特性を示す図である。起電力Vemfにδだけの過電圧を印加すると電流Iが流れる。このδによる電流の大きさを関連付ける特性図である。この特性は電極反応論から次式で一般化される。
δ1の時、電流はI1となり、その動作点での勾配が動的コンダクタンスとなり、更にその逆数が動的内部抵抗(Dir)となる。このDirに電流I1を乗じた値が電位差ΔVD1である。
FIG. 2 is a diagram showing an overvoltage-current characteristic in the embodiment according to the present invention. When an overvoltage of only δ is applied to the electromotive force Vemf , a current I flows. It is a characteristic diagram which correlates the magnitude of the current by this δ. This characteristic is generalized by the following equation from the electrode kinetics.
When δ 1 , the current becomes I 1 , the gradient at the operating point becomes the dynamic conductance, and its reciprocal becomes the dynamic internal resistance (Dir). The value obtained by multiplying this Dir by the current I 1 is the potential difference ΔV D1 .
また、δ2の時、電流はI2となり、その動作点での勾配が動的コンダクタンスとなり、更にその逆数が動的内部抵抗(Dir)となる。このDirに電流I2を乗じた値が電位差ΔVD2である。 Further, when δ 2 , the current becomes I 2 , the gradient at the operating point becomes the dynamic conductance, and the reciprocal thereof becomes the dynamic internal resistance (Dir). The value obtained by multiplying this Dir by the current I 2 is the potential difference ΔV D2 .
図3は、本発明に係る実施形態において、過電圧δに対する内部抵抗電位差ΔVD及び過電圧ΔVDの関係を示す図である。次式の関係式をグラフ化したものである。
図4は、本発明に係る実施形態において、容量に対する充填量の比率である蓄電比率SOCと起電力Vemfの関係を示すコバルト酸-カーボン電池の場合の関係を示す図である。実験値と理論式から表のまとめにしたがって数値計算したものである。 FIG. 4 is a diagram showing the relationship in the case of a cobalt acid-carbon battery showing the relationship between the storage ratio SOC, which is the ratio of the filling amount to the capacity, and the electromotive force Vemf in the embodiment according to the present invention. Numerical calculation is performed from experimental values and theoretical formulas according to the summary of the table.
図5は、電極種に依る移動度αと充電比率SOCに対する起電力Vemfの相関関係を示す図である。当該相関関係は、電極材料に依って異なる。コバルト酸、マンガン酸、ニッケル酸等の単独或は組み合わせによる正極とカーボンの負極という電極材料の構成が一般的である。充電比率SOC-起電力Vemf特性は基本的にはネルンストの式での反応移動度αが電池の材料構成によって異なる事による。図5に描かれる表は、論理と実験によって求めた一覧である。 FIG. 5 is a diagram showing the correlation between the mobility α depending on the electrode type and the electromotive force Vemf with respect to the charge ratio SOC. The correlation depends on the electrode material. Generally, an electrode material consisting of a positive electrode and a carbon negative electrode made of cobalt acid, manganese acid, nickel acid or the like alone or in combination is used. The charge ratio SOC-electromotive force Vemf characteristic is basically due to the fact that the reaction mobility α in the Nernst equation differs depending on the material composition of the battery. The table drawn in FIG. 5 is a list obtained by logic and experiment.
図6は、本発明に係る実施形態において、電池の性能を短時間で検知する手順を示すフローチャートである。 FIG. 6 is a flowchart showing a procedure for detecting the performance of the battery in a short time in the embodiment of the present invention.
本発明は、次の手順で課題解決のための手法を開発した。 The present invention has developed a method for solving a problem by the following procedure.
第1の手順として、電池内部での化学反応を物理化学によって解析し、種々の因子を洗い出した。ここでは、電池は、リチウムイオン電池などの二次電池であるものとして説明する。 As the first procedure, the chemical reaction inside the battery was analyzed by physical chemistry, and various factors were identified. Here, the battery will be described as being a secondary battery such as a lithium ion battery.
第2の手順として、電気等価回路網に置き換え、電気的計測可能な形式とした。 As the second procedure, it was replaced with an electrical equivalent circuit network to make it an electrically measurable format.
第3の手順として、外部回路との応答特性および整合性について基礎実験を踏まえ確認の上、検知性能を決定づける因子について短時間で抽出し、同定を可能とする計測回路の構築に成功した。以下、その概要を示す。 As the third procedure, after confirming the response characteristics and consistency with the external circuit based on the basic experiment, the factors that determine the detection performance were extracted in a short time, and the measurement circuit that enables identification was successfully constructed. The outline is shown below.
上記解析によって、電池内部等価回路は、図1に示す。 By the above analysis, the battery internal equivalent circuit is shown in FIG.
図1に示される電気等価回路において、ΔVDは、電極での酸化/還元反応の反応速度に起因する動的内部抵抗に電流を乗じた電位であり、次式で表される。
ここで、f=F/(RT)、F: ファラデー定数[C/mol]、R:空気定数[J/mol/T]、T:絶対温度[K]
In the electrical equivalent circuit shown in FIG. 1, ΔV D is a potential obtained by multiplying the dynamic internal resistance caused by the reaction rate of the oxidation / reduction reaction at the electrode by a current, and is expressed by the following equation.
Here, f = F / (RT), F: Faraday constant [C / mol], R: air constant [J / mol / T], T: absolute temperature [K].
なお、図1に示される等価回路において、電池の非動作時(充電も放電もしていない状態)では、電流は流れずに電池電圧は開放電圧(OCV)、略Vemfとなる。例えば、充電時には、このVemf(=η* eq)より高い電圧の外部電源をつなぎ、電池に電流を流し込む事になる。 In the equivalent circuit shown in FIG. 1, when the battery is not operating (in a state where neither charging nor discharging is performed), no current flows and the battery voltage is an open circuit voltage (OCV), which is approximately Vemf . For example, at the time of charging, an external power source having a voltage higher than this Vemf (= η * eq ) is connected, and a current is passed through the battery.
しかし、この電流のために、電池内部には内部抵抗が発生、電流を掛け合わせた電位差が生じ、これを加えた分(数7)だけ余分に電圧をあげ、さらに、微小電圧δを加えないと電流は流れないことになる。図3は、実際に電池端子に印加される電圧V-η*
eq=ΔVを縦軸に、横軸に真の過電圧δとの関係をグラフ化している。与えた電圧が、電池にとっての実際過電圧に、いかほど寄与するかが数7の式の恒等式から算出される。
However, due to this current, an internal resistance is generated inside the battery, and a potential difference is generated by multiplying the current. And the current will not flow. FIG. 3 graphs the relationship between the voltage V−η * eq = ΔV actually applied to the battery terminal on the vertical axis and the true overvoltage δ on the horizontal axis. How much the applied voltage contributes to the actual overvoltage for the battery is calculated from the identity of
電池を充電する過程においては、電池の起電力Vemfより高い電圧を印加し、始めて電池に充電電流が流れ充電される。しかし、実際に計測可能な電池端子間電圧Vは、電池内部の電池素子の持つ起電力Vemfに過電圧δを単純に加算されたものでなく、電流が流れることによる数6に示される反応抵抗による電位差が加算され数6の式となる。
ここでΔVは、計測可能であるが、その内容は電気化学理論に基づき解析的に算出され、いかなるで電池でも数6の式は、恒等的に成立する。ここで、ΔVは、過電圧(Over-Voltage),δは、真の過電圧(Intrinsic-excess-Voltage)と呼ばれる。
In the process of charging the battery, a voltage higher than the electromotive force Vemf of the battery is applied, and the charging current flows through the battery for the first time to be charged. However, the actually measurable voltage between the battery terminals V is not simply the addition of the overvoltage δ to the electromotive force Vemf of the battery element inside the battery, but the reaction resistance shown in Equation 6 due to the flow of current. The potential difference due to the above is added to obtain the equation of the number 6.
Here, ΔV is measurable, but its content is calculated analytically based on the electrochemical theory, and the equation of equation 6 holds uniformly in any battery. Here, ΔV is called an overvoltage (Over-Voltage), and δ is called a true overvoltage (Intinsic-excess-Voltage).
図1に示される電気内部等価回路においてΔVCは、電解質中の拡散、ポテンシャル場での泳動等に起因するカチオンの流れによって決まり、イオン二重層形成下、次式で表される。
電圧は電解質の固有の抵抗値と電流の積となる。
In the electric internal equivalent circuit shown in FIG. 1, ΔVC is determined by the flow of cations caused by diffusion in the electrolyte, migration in a potential field, etc., and is expressed by the following equation under the formation of an ion double layer.
The voltage is the product of the unique resistance of the electrolyte and the current.
以上より、電池に印加される電圧Vは次式が成立する。
即ち、電池に起電力(η*
eq)+過電圧(δ)を印加すると電池反応が起こり、その反応抵抗に依る電圧ドロップΔVD、電極界面に形成される電気二重層に依る電位差ΔVCとの総和となる。
From the above, the following equation holds for the voltage V applied to the battery.
That is, when an electromotive force (η * eq ) + overvoltage (δ) is applied to the battery, a battery reaction occurs, and the voltage drop ΔV D due to the reaction resistance and the potential difference ΔVC due to the electric double layer formed at the electrode interface. It becomes the sum.
この内ΔVCは、長期非動作からの計測時ではゼロであるから、計測立ち上がり時には次式が成立する。
上記で定義した過電圧δと電流Iの関係は次式の数11で表される。
数11の式の素因数をまとめ、数12の式、数13の式を定義する。
K00は、電池セルの固有な定数であり、電池の電極材料、構造によって決まり、次元は[C/mol]・[m/sec]・[m2]=[C/sec]/[mol/m3]、即ち、モル濃度あたりの電流となる。I0に関しては、sinh(δ×f/2)が過電圧の大きさによって決まる励起の大きさを決める因子で無次元、数13の式の中の、C*
rは、負極に蓄積しているモル濃度[mol/m3]を示し、従って、I0の次元はモル濃度[mol/m3]となる。
The relationship between the overvoltage δ and the current I defined above is expressed by the
The prime factors of the formula of the
K 00 is a unique constant of the battery cell, which is determined by the electrode material and structure of the battery, and the dimensions are [C / mol], [m / sec], [m 2 ] = [C / sec] / [mol / m 3 ], that is, the current per molar concentration. Regarding I 0 , sinh (δ × f / 2) is a factor that determines the magnitude of excitation determined by the magnitude of overvoltage. It is dimensionless, and C * r in the equation of equation 13 is accumulated in the negative electrode. It indicates the molar concentration [mol / m 3 ], and therefore the dimension of I 0 is the molar concentration [mol / m 3 ].
電池に蓄えることが出来る電気量である容量の時間積分となる。即ち、
定電流充電の場合、数13の式において、I0が一定であることは、その右辺が一定となる。あるC*
rの時、過電圧δはI0が一定値となるよう応じて変化する。C*
rの取りうる範囲は0~1であり、関数√(C*
r(1-C*
r)は、C*
r=0.5の時最大値0.5となる。この時のδ値が最小となり、一定値I0は
となる。
δと√(C*
r(1-C*
r)の関係は数13の式であり、過電圧δは、最大電流及び最大印加電圧から、その範囲に制限がかかり、その値をδmaxとすると、次式の数16が成立する。
このC*
r,max及びC*
r,minは、数16の右辺2式を解くことにより得られる。
即ち、充電における正極から負極へ時間Tをかけてのモル濃度の移動は、次式の数17で与えられる。
In the case of constant current charging, in the equation of Equation 13, that I 0 is constant means that the right side thereof is constant. At a certain C * r , the overvoltage δ changes according to the constant value of I 0 . The range that C * r can take is 0 to 1, and the function √ (C * r (1-C * r ) has a maximum value of 0.5 when C * r = 0.5. δ at this time. The value is the minimum, and the constant value I 0 is
Will be.
The relationship between δ and √ (C * r (1-C * r ) is the equation of Equation 13, and the overvoltage δ is limited in its range from the maximum current and the maximum applied voltage, and its value is δ max . , The number 16 of the following equation holds.
The C * r, max and C * r, min can be obtained by solving the two equations on the right side of the equation 16.
That is, the transfer of the molar concentration from the positive electrode to the negative electrode in charging over time T is given by the equation number 17.
容量Qは、モル移動単位I0に応じて移行比率が変わり、その積Q0が容量要素となり、これに電極固有定数K00を乗じた値となる。即ち、次式の数19となる。K00は、正極/負極の材質、それらの大きさによって決まる固有の係数であり、以下説明するように、この係数の大小によって、容量は決定づけられる。即ち、電池の性能である容量は、このK00に依存し、初期のK00が小さくなれば、性能が劣化した状態となり、K00を決める結晶の破壊度(有効結晶個数の低減)によって性能のSOH(State of Health)が決まることになる。
最大容量のための充電条件は次式の数20となり、その時の容量Qmaxは数21の式で与えられる。
上記K00は電極の性能を示す直接的な数値指標となるもので、この数値低減が容量の低減を示し、初期との比較は電池健全度(SOH)の指標となる。SOHは、基準を初期値とすれば現在の健全度を意味する。 The above K 00 is a direct numerical index indicating the performance of the electrode, and this numerical reduction indicates a reduction in capacity, and the comparison with the initial value is an index of battery soundness (SOH). SOH means the current soundness if the standard is the initial value.
SOCと起電力Vemfとの関係はネルンストの式より、次式の数17が成り立つ。ここで、式中αに関しては、酸化/還元反応速度の解析上、反応場の内外のGibbsポテンシャル差の活性度への影響度を示すもので、一般に移動度として定義づけられる係数である。数23は、この係数を導入したネルンスト式である。
また、過電圧δ-電流特性で重要な状態因数(SOC依存関数)は次式で導き出せる。
コバルト酸(Vs=3.6V)、二元系(Vs=3.7V)、3元系(Vs=3.8V)、いずれも、SOC10%では、Vemfは3.45と固定される。この実験値から数23、及び数24の補正定数αを確定される。図5に描かれた表は、実験値を数24に当てはめ計算によって、移動度αを求めたものである。
As for the relationship between the SOC and the electromotive force Vemf , the number 17 of the following equation holds from the Nernst equation. Here, α in the formula indicates the degree of influence of the Gibbs potential difference inside and outside the reaction field on the activity in the analysis of the oxidation / reduction reaction rate, and is a coefficient generally defined as mobility. Equation 23 is a Nernst equation that introduces this coefficient.
In addition, the state factor (SOC-dependent function) that is important for the overvoltage δ-current characteristic can be derived by the following equation.
Lithium cobalt oxide (V s = 3.6 V), binary system (V s = 3.7 V), ternary system (V s = 3.8 V), both fixed at 3.45 at SOC 10%. Will be done. From this experimental value, the correction constants α of the equation 23 and the equation 24 are determined. In the table drawn in FIG. 5, the mobility α is obtained by applying the experimental values to the equation 24 and calculating.
続いて、電池性能の瞬時計測方法の手法について説明する。 Next, the method of the instantaneous measurement method of the battery performance will be described.
最初に電池の開放電圧である起電力Vemfを計測する(S1)。Vemfは、外部から電池への電流の入出が無い状態での電池電圧であり、一般に、解放電圧OCV(Open Circuit Voltage)である。従って、この計測はインピーダンスの高い電圧計での計測値となる。 First, the electromotive force Beamf, which is the open circuit voltage of the battery, is measured (S1). Vemf is a battery voltage in a state where no current flows in and out of the battery from the outside, and is generally an open circuit voltage OCV (Open Circuit Voltage). Therefore, this measurement is a measured value with a voltmeter with high impedance.
次に、電池種のインプット情報として、電池の種類に基づいて、図5から該電池のパラメータであるVs及び移動度αを確定する(S2)。ここで、αは、正極の電極構造、多元素の場合には、混合比率、結晶楮によって決まる固有値であり、実験により決定される。 Next, as the input information of the battery type, Vs and the mobility α, which are the parameters of the battery, are determined from FIG. 5 based on the battery type (S2). Here, α is an eigenvalue determined by the electrode structure of the positive electrode, the mixing ratio in the case of multiple elements, and the crystal mulberry, and is determined experimentally.
次に、数23の式に基づいて、充電比率SOCに対応するCr *を算出する(S3)。SOCは、一般的に%で表示され、蓄電能力に対し、現在何%の電気量が蓄電されているかの指標となる。これは、負極に対し貯めこまれた還元剤の濃度、即ち、Cr *を%表示したものとなる。 Next, Cr * corresponding to the charge ratio SOC is calculated based on the equation of Equation 23 (S3). SOC is generally displayed in%, and is an index of what percentage of electricity is currently stored with respect to the storage capacity. This is a% display of the concentration of the reducing agent stored in the negative electrode, that is, Cr * .
計測値Vemfと、読み取り値α、Vsを使って算出されたSOCを、数24に代入しSOC依存関数値√(C* r(1-C* r)を算出する(S4)。 The SOC calculated using the measured value Emf and the readings α and Vs is substituted into the equation 24 to calculate the SOC-dependent function value √ (C * r (1-C * r ) (S4).
短時間での性能検査では、まず、起電力測定を行い、数24の式を適応し、蓄電状態SOCすなわち、Cr *を既知とし、この状態での、過電圧を印加して電流を計測し、電池の性能を確定することができる。 In the performance inspection in a short time, first, the electromotive force is measured, the equation of several 24 is applied, the storage state SOC, that is, Cr * is known, and the current is measured by applying the overvoltage in this state. , Battery performance can be determined.
次いで、起電力Vemfに対し過電圧ΔV1を加算して電池に印加したときに流れる電流I1を計測し、数3の式に基づいて、真の過電圧δ1を求める(S5)。 Next, the overvoltage ΔV 1 is added to the electromotive force V emf , the current I 1 flowing when applied to the battery is measured, and the true overvoltage δ 1 is obtained based on the equation of Equation 3 (S5).
次いで、前記起電力Vemfに対し過電圧ΔV2を加算して電池に印加したときに流れる電流I2を算出し、数4の式に基づいて、真の過電圧δ2を求める(S6)。
なお、S5,S6の工程では、過電圧δを与え電流Iを計測するが、数11の式に示すように電流Iは、電池の容量を左右する固有な係数のほか蓄電状態即ちSOCによっても√(C*
r(1-C*
r)の係数が関わって異なる。従って計測値はSOCが異なれば電流条件を固定とすれば、δ値も変える必要が生じる。逆に、このδを複数個設定し、電流計測値から、演算によって、電池性能係数K00が誘導できる。
Next, the overvoltage ΔV 2 is added to the electromotive force Vemf to calculate the current I 2 that flows when the
In the steps S5 and S6, the overvoltage δ is applied and the current I is measured. (The coefficient of C * r (1-C * r ) is different. Therefore, if the SOC is different, the δ value needs to be changed if the current condition is fixed. On the contrary, multiple δs are used. The battery performance coefficient K 00 can be derived by calculation from the set and current measurement values.
過電圧δに対する電流Iの式は数11で表される。この式を整理すると次式となり、
つまり、SOC(=C*
r×100)が既知であれば、過電圧に応じ電流値は、上式で決定する。今、過電圧δ1を与えた時、電流がI1である。過電圧δ2の時、電流がI2である。これは、上式を、いずれも満たすから、次式が得られる。
ここで、δ1、δ2は、1に対し微小な値ですから、マクロラン展開から、次式となる。
That is, if the SOC (= C * r × 100) is known, the current value is determined by the above equation according to the overvoltage. Now, when the overvoltage δ 1 is applied, the current is I 1 . When the overvoltage δ 2 is, the current is I 2 . Since this satisfies all of the above equations, the following equation is obtained.
Here, since δ 1 and δ 2 are minute values with respect to 1, the following equation is obtained from the macrorun expansion.
そして、数5に基づいて、各種パラメータ(C* r,I1,I2、δ1、δ2)を入力する(S7)。S7の工程により、K00が求められ、これにより、電池の性能評価値が確定される。 Then, various parameters (C * r , I 1 , I 2 , δ 1 , δ 2 ) are input based on the equation 5 (S7). By the step of S7, K00 is obtained, and the performance evaluation value of the battery is determined by this.
数12の式に示されるように、電極の素材によって決まる反応速度係数√(Kred/Kox)と電極の大きさによって決まるSからなり、このK00が分かれば、容量は、数20、数21の式から、印加の最大過電圧δmaxあるいは電流を求めるδminが分かっていれば、その条件設定で瞬時に、機械的に電池の容量を判定することができるという顕著な効果を奏する。 As shown in the equation of Eq. 12, it consists of a reaction rate coefficient √ (K red / K ox ) determined by the material of the electrode and S determined by the size of the electrode. If the maximum overvoltage δ max of the application or δ min for obtaining the current is known from the equation of the number 21, the remarkable effect that the capacity of the battery can be instantly and mechanically determined by setting the conditions is obtained.
真の過電圧δ1及びδ2に対し、電池の内部では電極反応を介して電流として応答し、該応答時間は電池状態によって異なり、応答時間を組み入れて電池性能係数K00を算出する。数8の式は時間経過に伴いゼロに収斂するため、数10の式となる。上記応答時間を組み入れて電池性能係数K00を算出する際には、電池状態が落ち着かない、即ち、まだ、電解質中のイオン、カチオン、アニオンが拡散運動中で、安定状態にない時にも、診断可能となる工夫を凝らしたことを特徴としている。数9の式の右辺第3項までは、ミリ秒オーダーでのレスポンスであるが、第4項は電池内に封じ込められている電解質中のイオンの拡散に関わり、動作を止めてから分、或は、時間オーダーの緩和時間となる。 The battery responds to the true overvoltages δ 1 and δ 2 as a current via an electrode reaction inside the battery, and the response time varies depending on the battery state, and the response time is incorporated to calculate the battery performance coefficient K00 . Since the equation of Eq. 8 converges to zero with the passage of time, it becomes the equation of Eq. 10. When calculating the battery performance coefficient K 00 by incorporating the above response time, the diagnosis is made even when the battery state is not stable, that is, the ions, cations, and anions in the electrolyte are still in a diffusion motion and are not in a stable state. It is characterized by elaborate ingenuity that makes it possible. Up to the third term on the right side of the equation of equation 9, the response is on the order of milliseconds, but the fourth term is related to the diffusion of ions in the electrolyte contained in the battery, and the operation is stopped for a minute or so. Is the relaxation time of the time order.
本発明によって、電池性能としての容量Qおよび現在の蓄電残量(SOC)を、短時間(1秒内)で確認できることから、電池生産での検査工程の時間短縮、生産設備の簡素化、機器実装での使用中の性能確認、更に、使用済み電池の良否確認、それに伴う処置・処理の速やかな決定が可能となり、電池使用の安全・安心につながり、電池の更なる広い適応につながり、世界人類の生活文化の発展向上に寄与するものとなる。 According to the present invention, the capacity Q as the battery performance and the current remaining charge (SOC) can be confirmed in a short time (within 1 second), so that the inspection process time in battery production can be shortened, the production equipment can be simplified, and the equipment can be confirmed. It is possible to check the performance during use in mounting, check the quality of used batteries, and promptly decide the treatment and processing associated with it, leading to the safety and security of battery use, leading to a wider range of battery adaptation, and the world. It will contribute to the development and improvement of human life and culture.
本発明は、電池を組み込んだ機器、電池の生産工程での品質管理、電池メーカの出荷検査、機器メーカの受け入れ時の性能チェック、等々、電池に関わる全てのステージで有用で、不可欠な計測手段として応用、活用されることとなる。このように、多岐にわたる電池利用のシーンそれぞれに適応した商品或は,システム装置の形態が考えられるが、本発明の基になる理論及びその理論の応用展開に関する手法は、共通であり、活用の場(シーン)に応じ装置、商品の実施形態となる。 The present invention is a useful and indispensable measuring means at all stages related to batteries, such as equipment incorporating a battery, quality control in the battery production process, shipping inspection of a battery manufacturer, performance check at the time of acceptance by an equipment manufacturer, and the like. It will be applied and utilized as. In this way, it is conceivable that the product or system device is suitable for each of a wide variety of battery usage scenes, but the theory underlying the present invention and the method for developing the application of the theory are common and utilized. It is an embodiment of the device and the product according to the place (scene).
I 電流、I0 モル移動単位、I1 電流、I2 電流、K00 電池性能係数、Q 容量、Vemf 起電力、α 移動度、δ 過電圧、δ1 過電圧、δ2 過電圧、δmax 過電圧、ΔV 過電圧、ΔV1 過電圧、ΔV2 過電圧、ΔVn 電池端子電圧。 I current, I 0 molar transfer unit, I 1 current, I 2 current, K 00 battery performance coefficient, Q capacity, Vemf electromotive force, α mobility, δ overvoltage, δ 1 overvoltage, δ 2 overvoltage, δ max overvoltage, ΔV Overvoltage, ΔV 1 overvoltage, ΔV 2 overvoltage, ΔVn Battery terminal voltage.
Claims (5)
前記電池の種類に基づいて、該電池のパラメータであるVs及び移動度αを求める工程と、
数1の式に基づいて、充電比率SOCに対応するCr *を算出する工程と、
数2の式に基づいて、SOC依存関数値を算出する工程と、
を備えることを特徴とする電池性能の瞬時計測方法。
A step of obtaining Vs and mobility α, which are the parameters of the battery, based on the type of the battery, and
The process of calculating Cr * corresponding to the charge ratio SOC based on the formula of Equation 1 and
The process of calculating the SOC-dependent function value based on the formula of Equation 2 and
A method for instantly measuring battery performance, which is characterized by being equipped with.
前記起電力Vemfに対し過電圧ΔV1を加算して前記電池に印加したときに流れる電流I1を算出する工程と、
前記起電力Vemfに対し過電圧ΔV2を加算して前記電池に印加したときに流れる電流I2を算出する工程と、
数3の式に基づいて、真の過電圧δ1を求める工程と、
数4の式に基づいて、真の過電圧δ2を求める工程と、
を備えることを特徴とする瞬時計測方法。
A step of adding an overvoltage ΔV 1 to the electromotive force V emf to calculate the current I 1 flowing when the overvoltage ΔV 1 is applied to the battery.
A step of adding an overvoltage ΔV 2 to the electromotive force V emf to calculate the current I 2 flowing when applied to the battery, and a step of calculating the current I 2.
The process of finding the true overvoltage δ 1 based on the equation of Eq. 3 and
The process of finding the true overvoltage δ 2 based on the equation of Eq. 4 and
An instantaneous measurement method characterized by being equipped with.
前記真の過電圧δ1及び前記真の過電圧δ2を計測し、電池の動作状態が正常であるか異常であるかを判定する工程を備えることを特徴とする電池性能の瞬時計測方法。 In the method for instantaneously measuring battery performance according to claim 2.
A method for instantaneously measuring battery performance, comprising a step of measuring the true overvoltage δ 1 and the true overvoltage δ 2 and determining whether the operating state of the battery is normal or abnormal.
数5の式に基づいて、電池性能係数K00を算出する工程を備えることを特徴とする電池性能の瞬時計測方法。
A method for instantaneously measuring battery performance, which comprises a step of calculating a battery performance coefficient K 00 based on the equation of the number 5.
前記真の過電圧δ1及び前記真の過電圧δ2に対し、前記電池の内部では電極反応を介して電流として応答し、該応答時間は電池状態によって異なり、前記応答時間を組み入れて電池性能係数K00を算出する工程を備えることを特徴とする電池性能の瞬時計測方法。
The method for instantaneously measuring battery performance according to any one of claims 2 to 4.
The true overvoltage δ 1 and the true overvoltage δ 2 are responded to as a current through an electrode reaction inside the battery, and the response time varies depending on the battery state. The response time is incorporated into the battery performance coefficient K. A method for instantaneously measuring battery performance, which comprises a step of calculating 00 .
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---|---|---|---|---|
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JP2017166874A (en) * | 2016-03-14 | 2017-09-21 | 株式会社東芝 | Storage battery evaluation device, storage battery, storage battery evaluation method, and program |
JP6589080B1 (en) * | 2019-01-15 | 2019-10-09 | ゴイク電池株式会社 | Deterioration degree of storage element and remaining storage capacity detection device |
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---|---|---|---|---|
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JP2017166874A (en) * | 2016-03-14 | 2017-09-21 | 株式会社東芝 | Storage battery evaluation device, storage battery, storage battery evaluation method, and program |
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