WO2017071123A1 - 正极活性材料表面包覆效果的检测方法 - Google Patents

正极活性材料表面包覆效果的检测方法 Download PDF

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WO2017071123A1
WO2017071123A1 PCT/CN2016/070760 CN2016070760W WO2017071123A1 WO 2017071123 A1 WO2017071123 A1 WO 2017071123A1 CN 2016070760 W CN2016070760 W CN 2016070760W WO 2017071123 A1 WO2017071123 A1 WO 2017071123A1
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active material
positive electrode
electrode active
tested
standard
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PCT/CN2016/070760
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English (en)
French (fr)
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王莉
何向明
庞小英
罗晶
李建军
尚玉明
吴英强
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江苏华东锂电技术研究院有限公司
清华大学
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Publication of WO2017071123A1 publication Critical patent/WO2017071123A1/zh
Priority to US15/954,597 priority Critical patent/US10274458B2/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4166—Systems measuring a particular property of an electrolyte
    • G01N27/4167—Systems measuring a particular property of an electrolyte pH
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4166—Systems measuring a particular property of an electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/4285—Testing apparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for detecting the surface coating effect of a positive electrode active material.
  • the structure and performance of the positive active material are the key factors affecting the electrochemical performance improvement of lithium ion batteries.
  • the development of high performance positive active materials has become a research hotspot.
  • the positive active material When in contact with a large area of the electrolyte, the positive active material is prone to the dissolution of the main element, which greatly affects the stability and performance of the positive active material.
  • Surface coating by the positive active material is a commonly used method in the prior art to solve the problem.
  • the detection of the coating effect of the positive electrode active material is generally tested by the electrical properties of the battery, thereby indirectly judging. The period of such indirect judgment is long, and the influence of the battery preparation process and other battery materials on the performance of the battery cannot be ruled out.
  • Another method for detecting the surface coating effect of the positive electrode active material is to observe the coated material by scanning electron microscopy, and directly determine the coating effect.
  • the method is not only costly, but can only be carried out during the detection process. Micro-analysis makes it difficult to objectively reflect the overall coating effect of the positive active material.
  • the detection method of the present invention indirectly reflects the dissolution rate of metal ions in the positive electrode active material by the pH value of the liquid phase of the solid-liquid mixture or the concentration of the metal ion, by comparing the coated positive electrode active material to be tested with the standard package.
  • the surface coating effect of the coated positive electrode active material to be tested is detected by the pH value or the metal ion concentration of the positive electrode active material.
  • the detection method can objectively reflect the overall coating effect of the surface of the positive electrode active material, which is not only simple and effective, but also low in cost.
  • 1 is a first embodiment of the present invention, an uncoated nickel-nickel-cobalt-manganese ternary active material, and a lithium aluminum oxide-coated nickel-cobalt-manganese ternary active material at a temperature of 30 ° C and a concentration of A plot of the pH versus time curve for a 0.03 m/L nitric acid reaction.
  • FIG. 2 is a first embodiment of the present invention, an uncoated nickel-nickel-cobalt-manganese ternary active material, and a lithium aluminum oxide-coated nickel-cobalt-manganese ternary active material at a temperature of 30 ° C and a concentration of A plot of the pH versus time curve for a 0.03 m/L hydrochloric acid reaction.
  • FIG. 3 is a first embodiment of the present invention, an uncoated nickel-nickel-cobalt-manganese ternary active material, and a lithium aluminum oxide-coated nickel-cobalt-manganese ternary active material at a temperature of 30 ° C and a concentration of A plot of the pH versus time curve for the 0.03 m/L acetic acid reaction.
  • nickel-nickel-cobalt-manganese ternary active material having a coating mass ratio of 1% and a standard nickel-cobalt-manganese ternary positive electrode active agent having a coating mass ratio of 1% according to the first embodiment of the present invention
  • Embodiments of the present invention provide a method for detecting a surface coating effect of a positive electrode active material, which includes the following steps:
  • the predetermined concentration of the acid solution ranges from 0.01 mol/L to 0.5 mol/L
  • the acid solution may be a strong acid such as hydrochloric acid, nitric acid or sulfuric acid, or a weak acid such as acetic acid, oxalic acid or propionic acid.
  • the predetermined concentration of the acid solution can be measured by a method commonly used in the art, such as a pH meter or an acid-base titration. Specifically, the method of calibrating the acid solution comprises the following steps:
  • the NaOH solution is calibrated with potassium hydrogen phthalate; the purpose of calibrating the acid solution with the calibrated NaOH solution is to obtain the actual concentration of the acid solution, and to ensure the pH and the standard to be tested.
  • the predetermined concentration of the acid solution used in the pH determination process is the same, and the pH error is reduced.
  • the concentration of the acid solution is in the range of 0.01 mol/L to 0.09 mol/L
  • the calibration is performed with 0.01 mol/L NaOH
  • the acid solution ranges from 0.1 mol/L to 0.5 mol/L
  • the calibration is performed with 0.1 mol/L NaOH.
  • the solid-liquid ratio of the coated positive electrode active material to be tested and the acid solution ranges from 1:1000 to 1:1, and the solid-liquid ratio refers to the mass of the coated positive electrode active material to be tested and the acid solution.
  • the proportion of the volume means that the surface of the positive electrode active material has a coating, and the positive electrode material may be a lithium transition metal oxide such as lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide ternary active material, etc.
  • the coating may be one of various inorganic or organic substances such as aluminum oxide, calcium phosphide or calcium phosphate.
  • the coating does not chemically react with the acid solution.
  • the coated positive electrode active material to be tested is completely immersed in the acid solution in order to make the coated positive electrode active material to be tested sufficiently contact with the acid solution, and the positive electrode active material dissolves metal ions in the acid solution, thereby making the acid solution
  • the pH value changes, and the coating can reduce the reaction of the metal ion elution. Therefore, the surface coating effect of the coated positive electrode active material to be tested may cause different metal ion dissolution rates in the positive electrode active material.
  • a pH meter probe and a thermometer may be further inserted into the first solid-liquid mixture.
  • the pH meter is used to read the pH value of the liquid phase in the first solid-liquid mixture at any time, thereby indirectly reflecting the dissolution rate of metal ions in the positive electrode active material; the thermometer is used to control the temperature during the detection process, so that the heating is The temperature is kept constant during the stirring, and the heating temperature may range from 0 °C to 80 °C.
  • the container is sealed to prevent evaporation of the acid solution during the detection; the solid-liquid mixture is heated and stirred in order to allow the acid solution to sufficiently and uniformly contact the coated positive active material to be tested.
  • the heating mode is water bath heating, and the stirring mode is uniform stirring.
  • the pH count value is read every 1 min to 150 min while heating and stirring, and the interval time can be determined according to the reaction rate of the acid solution and the coated positive electrode active material to be tested.
  • the standard pH value is an artificially defined reference value
  • the standard pH value determining method is substantially the same as the above steps S1 to S4, and the difference is only replaced by the coated positive electrode active material to be tested.
  • the coated positive electrode active material, specifically, the standard pH value is determined as follows:
  • the acid solution is the same as the type of the acid solution used in the step S1 and the predetermined concentration thereof;
  • the standard pH value is determined by reacting a standard coated positive electrode active material with an acid solution, and it is ensured that the determination process of the standard pH value and the determination process of the pH value to be tested are performed under the same reaction conditions, and the same reaction condition is performed. It means that the chemical composition and quality of the positive active material are the same, the type of the acid solution and its concentration are the same, and the heating temperature is the same. Preferably, the chemical composition of the coating is the same, and more preferably, the quality of the coating is also the same.
  • the standard coated positive electrode active material is an artificially selected coated positive electrode active material which is considered to have a satisfactory coating effect, and is used as a standard for evaluating the coating effect, and is superior to the coating of the coated positive electrode active material.
  • the coating effect is good, and the coating of the coated positive electrode active material which is inferior to the standard is considered to be poor in coating effect.
  • a person skilled in the art can determine the surface coating condition of the coated positive electrode active material of the standard by a scanning electron microscope apparatus.
  • the standard coated positive active material is a coated positive active material which has good safety, low self-discharge rate and high temperature stability when applied to a lithium ion battery.
  • the standard pH value includes a series of pH values that change with time, and the pH value of the positive electrode active material and the acid solution during the reaction process approaches a maximum value. Therefore, the S5 step may further include:
  • A1, A2 and A3 indicate that the uncoated nickel-cobalt-manganese ternary active material has a concentration of 0.03 m/L of nitric acid and hydrochloric acid at a temperature of 30 °C.
  • B1, B2, B3 means that the nickel-cobalt-manganese ternary positive electrode active material coated with aluminum oxide is respectively at a temperature of 30 ° C and a concentration of 0.03 m / L of nitric acid
  • the curve of pH value with time in the reaction of hydrochloric acid and acetic acid shows that the uncoated nickel-cobalt-manganese ternary active material and the nickel-cobalt-manganate ternary coated with aluminum oxide under the same conditions can be seen.
  • the pH of the positive active material at the same time is different, and the pH of the nickel-cobalt-manganese ternary active material coated with aluminum oxide at the same time is lower than the pH of the uncoated nickel-cobalt-manganese ternary active material. value. It can be seen that the coating effect can be reflected in the pH value of the liquid phase in the solid-liquid mixture, that is, the surface coating effect of the positive electrode active material can be reflected by the pH value change of the acid solution.
  • the acid solution is an acetic acid solution.
  • the difference from the first embodiment is that 10 g of lithium nickel cobalt manganese oxide ternary active material coated with different processes and having a mass ratio of 1% of aluminum oxide is weighed, and the PH count value is recorded as the pH value to be measured 2, and the comparison is made.
  • the pH value to be tested is 2 and the standard pH value.
  • the same coating effect of 10 g of the nickel-cobalt-manganese ternary positive electrode active material coated with the mass ratio of 1% of aluminum oxide causes different pH values in the solid-liquid mixture, with the reaction time.
  • the pH value to be tested in the embodiment the pH value to be measured 2
  • the standard pH value all approach a maximum value.
  • the maximum pH value in Example 1 is 6.9
  • the maximum pH value in Example 2 is 4.82
  • the standard pH maximum is 5.09. It can be seen that the coating effect of the aluminum oxide in the first embodiment is relative to the standard aluminum oxide package.
  • the coating effect is not good, and the coating effect of the aluminum oxide in the second embodiment is better than that of the standard aluminum oxide, so that it can be judged that the three kinds of 10 g coating have a mass ratio of 1% of aluminum oxide.
  • the coating effect of Example 2 was the best in the lithium nickel cobalt manganese oxide ternary positive electrode active material.
  • Another embodiment of the present invention provides a method for detecting the surface coating effect of a positive electrode active material.
  • the difference between the detection method and the first embodiment is to compare various metal ion concentrations of the liquid phase in the solid-liquid mixture with standard metal ions.
  • the surface coating effect of the positive electrode active material was detected by the concentration. Specific steps are as follows:
  • the metal ion concentration in the liquid phase of the third solid-liquid mixture is recorded every 10 min to 150 min, and the interval time can be determined according to the reaction rate of the acid solution and the coated positive electrode active material to be tested.
  • the concentration of various metal ions in the liquid phase of the third solid-liquid mixture can be measured by a conventional method such as flame atomic absorption or plasma photoelectric direct reading spectrometer.
  • the standard metal ion concentration is an artificially defined reference value, and the method for determining the standard metal ion concentration is substantially the same as the above steps S1 to S4, and the difference is only in the coated positive electrode active to be tested.
  • the material is replaced by a standard coated positive active material.
  • the standard metal ion concentration is determined as follows:
  • the acid solution is the same as the type of the acid solution used in the step S1 and the concentration thereof;
  • the standard metal ion concentration is determined by reacting a standard coated positive electrode active material with an acid solution, and it is required to ensure that the process of determining the concentration of the standard metal ion and the process of determining the concentration of the metal ion to be tested are performed under the same reaction conditions.
  • the same reaction conditions mean that the chemical composition and mass of the positive electrode active material are the same, the type of the acid solution and its concentration are the same, and the heating temperature is the same.
  • the chemical composition of the coating is the same, and more preferably, the quality of the coating is also the same.
  • the standard coated positive electrode active material is an artificially selected coated positive electrode active material which is considered to have a satisfactory coating effect, and is used as a standard for evaluating the coating effect, and is superior to the coating of the coated positive electrode active material. It is considered that the coating effect is good, and the coating of the coated positive electrode active material which is inferior to the standard is considered to be poor in coating effect.
  • a person skilled in the art can determine the surface coating condition of the coated positive electrode active material of the standard by a scanning electron microscope apparatus.
  • the standard coated positive active material is a coated positive active material which has good safety, low self-discharge rate and high temperature stability when applied to a lithium ion battery.
  • the standard metal ion concentration includes a series of metal ion concentrations that vary with time, and the metal ion concentration during the reaction of the positive active material with the acid solution approaches a maximum value. Therefore, the S5 step may further include:
  • the rate of change of the metal ion concentration to be measured during the detection process is less than the rate of change of the standard metal ion concentration, it is judged that the reaction rate of the positive electrode active material to be tested and the acid solution is slow, and the coated positive electrode active material to be tested is coated. The effect is good, otherwise the coating effect is not good.
  • NCM nickel-cobalt-manganese-lithium ternary active material
  • NCM-Al 2 O 3 lithium aluminum cobalt-cobalt ternary active material coated with aluminum oxide.
  • the concentration of various metal ions in the liquid phase of the solid-liquid mixture after the material (NCM) and the nickel-cobalt-manganese ternary positive active material (NCM-Al 2 O 3 ) coated with aluminum oxide was 30 min; It is indicated that 0.03 m/L of acetic acid is respectively immersed in uncoated nickel-cobalt-manganese-lithium ternary active material (NCM) and lithium aluminum cobalt-cobalt ternary active material (NCM-Al 2 O coated with aluminum oxide) 3 )
  • the uncoated nickel-cobalt-manganese ternary active material under the same conditions and the nickel-cobalt-manganese ternary active material coated with aluminum oxide have different metal ion concentrations at the same time, and at the same time.
  • the metal ion concentration of the nickel-cobalt-manganese ternary positive electrode active material coated with aluminum oxide is smaller than the metal ion concentration of the uncoated nickel-cobalt-manganese ternary positive electrode active material.
  • the coating effect can be reflected in the metal ion concentration of the liquid phase in the solid-liquid mixture, that is, the surface coating effect of the positive electrode active material can be reflected by the change of the metal ion concentration in the liquid phase of the solid-liquid mixture.
  • the acid solution is an acetic acid solution.
  • the mol/L acetic acid solution was added to the above three-necked flask to soak the nickel-cobalt-manganate, the pH meter probe and the thermometer were inserted into the three-necked flask and sealed, and the mixture was heated at 25 ° C in a water bath and stirred at a constant rate for 120 minutes.
  • the solid-liquid mixture is taken once, and the concentration of the metal ions in the solid-liquid mixture is measured by flame atomic absorption, that is, the concentration of the metal ion to be tested is 1; after that, 10 g is weighed and observed by scanning electron microscopy, and the coating effect is good and coated.
  • the nickel-cobalt-manganese ternary positive electrode active material with a mass ratio of 1% of aluminum oxide was subjected to the same experimental procedure as above, and the solid-liquid mixture was taken once after 120 minutes, and measured by flame atomic absorption.
  • the difference from the first embodiment is that 10 g of a nickel-cobalt-manganese ternary positive electrode active material coated with a mass ratio of 1% of aluminum oxide by different processes is weighed, and the metal ion concentration in the solid-liquid mixed solution is recorded as a test. The metal ion concentration is 2, and the metal ion concentration 2 to be measured and the standard metal ion concentration are compared.
  • Example 1 The metal ion concentration to be measured in Example 1, the metal ion concentration to be measured in Example 2, and the standard metal ion concentration in Example 2 were measured, and the measurement data are shown in the following table:
  • the same 10 g of lithium nickel cobalt manganese oxide ternary active material coated with a mass ratio of 1% of aluminum oxide has different coating effects, resulting in metal ions in the liquid phase of the solid-liquid mixture.
  • the concentration is different.
  • the Li ion concentration, the Ni ion concentration, the Co ion concentration, and the Mn ion concentration are respectively larger than the corresponding standard metal ion concentration, and it is judged that the coating effect of the aluminum oxide in the first embodiment is higher than that of the standard aluminum oxide.
  • the coating effect is poor; in Example 2, the Li ion concentration, the Ni ion concentration, the Co ion concentration, and the Mn ion concentration are respectively smaller than the corresponding standard metal ion concentration, and the coating effect of the aluminum oxide in the second embodiment is judged to be higher than the standard. The effect of the aluminum oxide coating is good.
  • the method for detecting the surface coating effect of the positive electrode active material of the present invention detects the coating effect of the surface of the positive electrode active material according to the pH value of the solution after the reaction of the acid solution and the coated positive electrode active material or the concentration of various metal ions in the solution after the reaction, the detection
  • the method is low in cost, simple and effective, and can meet the needs of production and scientific research work, and can be used for detecting the surface coating effect of the sample.

Abstract

一种正极活性材料表面包覆效果的检测方法，包括：提供一预定浓度的酸溶液；将待测的包覆正极活性材料放置于一容器；将所述酸溶液加入所述容器直至完全浸泡该待测的包覆正极活性材料，形成一第一固液混合物；密封上述容器，加热并搅拌所述第一固液混合物，同时记录不同时间所述第一固液混合物中液相的pH值；通过比较所述第一固液混合物中液相pH值与标准pH值判断该待测的包覆正极活性材料的表面包覆效果。该检测方法还可以通过测量固液混合物中的金属离子浓度来检测正极活性材料的表面包覆效果。

Description

正极活性材料表面包覆效果的检测方法 技术领域
本发明涉及一种正极活性材料表面包覆效果的检测方法。
背景技术
正极活性材料的结构与性能是影响锂离子电池电化学性能提升的关键因素，目前，开发高性能的正极活性材料已成为研究的热点。在与电解液大面积接触时，正极活性材料易出现主元素溶解流失等现象，极大的影响了正极活性材料的稳定和性能的发挥。而通过对正极活性材料进行表面包覆是现有技术中解决所述问题普遍采用的方法。然而，现有技术中对正极活性材料包覆效果的检测一般是通过电池的电性能进行测试，从而间接判断。而这种间接判断的周期较长，且无法排除电池制备工艺和其他电池材料对电池性能的影响，因此在实际应用中仍然无法实现对正极活性材料包覆效果的准确判定。另一种对正极活性材料表面包覆效果的检测方法是通过扫描电镜对包覆后的材料进行观察，直接对包覆效果进行判定，然而，该方法不仅成本高昂，且检测过程中只能进行微区分析，难以客观反应正极活性材料的整体包覆效果。
发明内容
有鉴于此，确有必要提供一种低成本、简单有效的正极活性材料表面包覆效果的检测方法。
一种正极活性材料表面包覆效果的检测方法，包括：
S1，提供一预定浓度的酸溶液；
S2，将待测的包覆正极活性材料放置于一容器；
S3，将所述酸溶液加入所述容器直至完全浸泡该待测的包覆正极活性材料，形成一第一固液混合物；
S4，密封上述容器，加热并搅拌所述第一固液混合物，同时记录不同时间所述第一固液混合物中液相的pH值，即待测pH值；以及
S5，通过比较所述待测pH值与标准pH值判断该待测的包覆正极活性
材料的表面包覆效果。
一种正极活性材料表面包覆效果的检测方法，包括：
S1，提供一预定浓度的酸溶液；
S2，将待测的包覆正极活性材料放置于一容器；
S3，将所述酸溶液加入所述容器直至完全浸泡该待测的包覆正极活性材料，形成一第一固液混合物；
S4，密封上述容器，加热并搅拌所述第一固液混合物，同时记录不同时间所述第一固液混合物液相中各种金属离子的浓度，即待测金属离子浓度；以及
S5，通过比较所述待测金属离子浓度与标准金属离子浓度的大小判断所述待测的包覆正极活性材料的表面包覆效果。
与现有技术比较，本发明检测方法通过固液混合物液相的pH值或金属离子浓度大小来间接反映正极活性材料中金属离子溶出速率，通过比较待测的包覆正极活性材料与标准的包覆正极活性材料的pH值或金属离子浓度检测待测的包覆正极活性材料的表面包覆效果。该检测方法能够客观地反映正极活性材料表面的整体包覆效果，不仅简单有效，而且成本较低。
 附图说明
图1为本发明第一实施例中未包覆的镍钴锰酸锂三元正极活性材料、包覆三氧化二铝的镍钴锰酸锂三元正极活性材料在温度30℃分别与浓度为0.03m/L的硝酸反应时pH值随时间变化的曲线对比图。
图2为本发明第一实施例中未包覆的镍钴锰酸锂三元正极活性材料、包覆三氧化二铝的镍钴锰酸锂三元正极活性材料在温度30℃分别与浓度为0.03m/L的盐酸反应时pH值随时间变化的曲线对比图。
图3为本发明第一实施例中未包覆的镍钴锰酸锂三元正极活性材料、包覆三氧化二铝的镍钴锰酸锂三元正极活性材料在温度30℃分别与浓度为0.03m/L的醋酸反应时pH值随时间变化的曲线对比图。
图4为本发明第一实施例中两种包覆质量比为1%的镍钴锰酸锂三元正极活性材料及标准的包覆质量比为1%的镍钴锰酸锂三元正极活性材料分别与醋酸反应时pH值随时间变化的曲线对比图。
具体实施方式
下面将结合附图及具体实施例对本发明提供的正极活性材料表面包覆效果的检测方法作进一步的详细说明。
本发明实施例提供一种正极活性材料表面包覆效果的检测方法，其包括以下步骤：
S1，提供一预定浓度的酸溶液；
S2，将待测的包覆正极活性材料放置于一容器；
S3，将所述酸溶液加入所述容器直至完全浸泡所述待测的包覆正极活性材料，形成一第一固液混合物；
S4，密封上述容器，加热并搅拌所述第一固液混合物，同时记录不同时间所述第一固液混合物中液相的pH值，即待测pH值；以及
S5，通过比较所述待测pH值与一标准pH值来判断所述待测的包覆正极活性材料的表面包覆效果。
该S1步骤中，该酸溶液的预定浓度范围为0.01 mol/L～0.5mol/L，该酸溶液可以为强酸，如盐酸、硝酸或硫酸，也可以为弱酸，如醋酸、草酸或丙酸。该酸溶液的预定浓度可以通过现有技术中常用方法测量，如pH计或酸碱滴定。具体的，标定所述酸溶液的方法包括以下步骤：
S11，配置一酸溶液；
S12，提供一已标定的NaOH溶液，将该已标定的NaOH溶液分别缓慢滴入三份上述酸溶液中，同时用pH计监测，直到pH值为7时均停止滴定NaOH溶液，分别计算得到该三份酸溶液的浓度，三份酸溶液相对平均偏差应小于0.2%，取三份酸溶液浓度的平均值作为该酸溶液的已知浓度。
该S12步骤中，优选地，采用邻苯二甲酸氢钾标定所述NaOH溶液；采用已标定的NaOH溶液标定所述酸溶液的目的是为了得到酸溶液的实际浓度，保证待测pH值与标准pH值确定过程中所用酸溶液的预定浓度相同，减小pH值误差。优选地，酸溶液浓度范围为0.01mol/L～0.09mol/L时采用0.01mol/L的NaOH标定，酸溶液范围为0.1mol/L～0.5mol/L时采用0.1mol/L的NaOH标定。
该S3步骤中，该待测的包覆正极活性材料与酸溶液的固液比范围为1：1000～1：1，所述固液比是指待测的包覆正极活性材料质量与酸溶液体积的比例。该“包覆正极活性材料”是指正极活性材料表面具有包覆物，该正极材料可以为锂过渡金属氧化物，如钴酸锂、锰酸锂、镍钴锰酸锂三元正极活性材料等中的至少一种，该包覆物可以为各种无机物或有机物，如三氧化二铝、磷化钙或磷酸钙等中的一种。优选的，该包覆物不与酸溶液发生化学反应。
该待测的包覆正极活性材料完全浸泡在该酸溶液中是为了使待测的包覆正极活性材料充分与酸溶液接触，正极活性材料在酸溶液中会溶出金属离子，从而使酸溶液的pH值发生变化，而包覆物则能够减小这种金属离子溶出的反应，因此该待测的包覆正极活性材料的表面包覆效果不同会导致该正极活性材料中金属离子溶出速率不同。
该S4步骤中，可以进一步在所述第一固液混合物中插入pH计探头及温度计。该pH计用于随时读取所述第一固液混合物中液相的pH值，从而间接反映正极活性材料中金属离子的溶出速率；该温度计用于控制检测过程中的温度，使该加热并搅拌过程中温度保持恒定，该加热温度范围可以为0°C～80°C。
密封所述容器是为了防止检测过程中酸溶液挥发；加热并搅拌所述固液混合物是为了使酸溶液能够与待测的包覆正极活性材料充分且均匀接触。优选的，该加热方式为水浴加热，该搅拌方式为匀速搅拌。在加热搅拌的同时每隔1min～150min读取一次pH计数值，该间隔时间可以根据酸溶液与待测的包覆正极活性材料反应速率自行确定。
该S5步骤中，该标准pH值是人为规定的一对比参照值，所述标准pH值确定方法与上述步骤S1~S4基本相同，区别仅在所述待测的包覆正极活性材料替换成标准的包覆正极活性材料，具体的，所述标准pH值确定方法如下：
S51，提供所述预定浓度的酸溶液，该酸溶液与上述S1步骤中所用的酸溶液种类及其预定浓度相同；
S52，将标准的包覆正极活性材料放置于一容器；
S53，将所述酸溶液加入所述容器直至完全浸泡该标准的包覆正极活性材料，形成一第二固液混合物；以及
S54，密封上述容器，加热并搅拌所述第二固液混合物，同时记录不同时间所述第二固液混合物中液相的pH值，即标准pH值，该加热温度与上述S4步骤的加热温度相同。
该标准pH值是采用标准的包覆正极活性材料与酸溶液反应确定，需确保该标准pH值的确定过程与所述待测pH值的确定过程是在同等反应条件进行，所述同等反应条件是指正极活性材料化学组成及质量相同，酸溶液种类及其浓度相同，并且加热温度相同。优选的，所述包覆物的化学组成相同，更优选地，所述包覆物的质量也相同。所述标准的包覆正极活性材料为人为选择出的被认为具有合格的包覆效果的包覆正极活性材料，作为评价包覆效果的标准，优于该标准的包覆正极活性材料的包覆被认为是包覆效果好，差于该标准的包覆正极活性材料的包覆被认为是包覆效果差。本领域技术人员可通过扫描电镜仪器确定该标准的包覆正极活性材料的表面包覆状况。优选地，该标准的包覆正极活性材料为应用于锂离子电池时安全性好、自放电率低、高温稳定性好的包覆正极活性材料。
该标准pH值包括随时间变化的一系列的pH值，并且正极活性材料与酸溶液反应过程中pH值趋近于一最大值，因此，该S5步骤可进一步包括：
当待测pH最大值小于标准pH最大值时，则判断待测的包覆正极活性材料中金属离子的溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差；或
当同一时刻待测pH值小于标准pH值时，则判断该待测的包覆正极活性材料中金属离子的溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差；又或
当检测过程中待测pH值变化速率小于标准pH值变化速率时，则判断该待测的正极活性材料与酸溶液反应速度较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差。
如图1、图2、图3所示，其中A1、A2、A3表示未包覆的镍钴锰酸锂三元正极活性材料在温度30℃时分别与浓度为0.03m/L的硝酸、盐酸、醋酸反应中pH值随时间变化的曲线图，B1、B2、B3表示包覆三氧化二铝的镍钴锰酸锂三元正极活性材料在温度30℃时分别与浓度0.03m/L的硝酸、盐酸、醋酸反应中pH值随时间变化的曲线图，可见，在同等条件下未包覆的镍钴锰酸锂三元正极活性材料与包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料在同一时间的pH值不同，且同一时间包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料的pH值小于未包覆的镍钴锰酸锂三元正极活性材料pH值。由此可见，包覆效果可以体现在固液混合物中液相的pH值上，即，通过酸溶液的pH值变化可以反映正极活性材料的表面包覆效果。
实施例1
本实施例中酸溶液为醋酸溶液。
称取0.4gNaOH溶解于100ml去离子水中，定容稀释至1000ml，称取2.04g邻苯二甲酸氢钾加水溶解，用所述NaOH溶液滴定该邻苯二甲酸氢钾溶液；用已标定的NaOH溶液进行滴定一醋酸溶液测得醋酸实际浓度；称取10g包覆有质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料于三口烧瓶中，量取100ml浓度为0.03mol/L的醋酸溶液浸泡上述三口烧瓶中所述镍钴锰酸锂三元正极活性材料，在该三口烧瓶插入PH计探头及温度计且密封，水浴25°C加热及匀速搅拌所述三口烧瓶中的固液混合物，同时每隔1min记录一次PH计数值，即待测pH值1；之后，称取10g通过扫描电镜观察认为包覆效果好且包覆有质量比1%三氧化二铝的镍钴锰酸锂三元正极活性材料，进行上述同样的实验过程，并每隔1min记录一次PH计数值，即标准pH值，比较所述待测pH值1与标准pH值大小。
实施例2
与实施例1的区别为称取10g采用不同工艺包覆的质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料，记录PH计数值为待测pH值2，比较该待测pH值2与标准pH值大小。
如图4所示，同样10g包覆有质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料的包覆效果不同引起固液混合物中pH值不同，随着反应时间的增加，实施例中的待测pH值1、待测pH值2及标准pH值均趋近于一最大数值。实施例1中最大pH值为6.9，实施例2中最大pH值为4.82，标准pH最大值为5.09，可见，实施例1中三氧化二铝的包覆效果相对于标准的三氧化二铝包覆效果不好，实施例2中三氧化二铝的包覆效果相对于标准的三氧化二铝的包覆效果好，由此可以判断3种10g包覆有质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料中实施例2的包覆效果最好。
本发明另一实施例提供一种正极活性材料表面包覆效果的检测方法，该检测方法与第一实施例的区别是通过比较固液混合物中液相的各种金属离子浓度与标准的金属离子浓度来检测出正极活性材料的表面包覆效果。具体步骤如下：
S1，提供一预定浓度的酸溶液；
S2，将待测的包覆正极活性材料放置于一容器；
S3，将所述酸溶液加入所述容器直至完全浸泡该待测的包覆正极活性材料，形成一第三固液混合物；
S4，密封上述容器，加热并搅拌所述第三固液混合物，同时记录不同时间所述第三固液混合物液相中各种金属离子的浓度，即待测金属离子浓度；以及
S5，通过比较所述待测金属离子浓度与标准金属离子浓度判断待测的包覆正极活性材料的表面包覆效果。
该S4步骤中，每隔10min～150min记录一次所述第三固液混合物液相中的金属离子浓度，该间隔时间可以根据酸溶液与待测的包覆正极活性材料反应速率自行确定。该第三固液混合物液相中各种金属离子浓度可以采用常规方法测量，如火焰原子吸收或等离子体光电直读光谱仪。
该S5步骤中，该标准金属离子浓度大小是人为规定的一对比参照值，所述标准金属离子浓度的确定方法与上述步骤S1~S4基本相同，区别仅在所述待测的包覆正极活性材料替换成标准的包覆正极活性材料，具体的，所述标准金属离子浓度的确定方法如下：
S51，提供所述预定浓度的酸溶液, 该酸溶液与上述S1步骤中所用的酸溶液种类及其浓度相同；
S52，将标准的包覆正极活性材料放置于一容器；
S53，将所述酸溶液加入所述容器直至完全浸泡所述标准的包覆正极活性材料，形成一第四固液混合物；以及
S54，密封上述容器，加热并搅拌所述第四固液混合物，同时记录不同时间所述第四固液混合物液相中各种金属离子浓度，即标准金属离子浓度, 该加热温度与上述S4步骤的加热温度相同。
该标准金属离子浓度是采用标准的包覆正极活性材料与酸溶液反应确定，需确保该标准金属离子浓度的确定过程与所述待测金属离子浓度的确定过程是在同等反应条件进行，所述同等反应条件是指正极活性材料化学组成及质量相同，酸溶液种类及其浓度相同，并且加热温度相同。优选的，所述包覆物的化学组成相同，更优选地，所述包覆物的质量也相同。所述标准的包覆正极活性材料为人为选择出的被认为具有合格的包覆效果的包覆正极活性材料，作为评价包覆效果的标准，优于该标准的包覆正极活性材料的包覆被认为是包覆效果好，差于该标准的包覆正极活性材料的包覆被认为是包覆效果差。本领域技术人员可通过扫描电镜仪器确定该标准的包覆正极活性材料的表面包覆状况。优选地，该标准的包覆正极活性材料为应用于锂离子电池时安全性好、自放电率低、高温稳定性好的包覆正极活性材料。
该标准金属离子浓度包括随时间变化的一系列的金属离子浓度，并且正极活性材料与酸溶液反应过程中金属离子浓度趋近于一最大值，因此，该S5步骤可进一步包括：
当待测金属离子浓度的最大值小于标准金属离子浓度的最大值时，则判断待测的包覆正极活性材料中金属离子溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果不好；或
当同一时刻待测金属离子浓度小于标准金属离子浓度时，则判断该待测的包覆正极活性材料中金属离子溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果不好；又或
当检测过程中待测金属离子浓度的变化速率小于标准金属离子浓度的变化速率时，则判断该待测的正极活性材料与酸溶液反应速度较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果不好。
如表1所示，表示0.03m/L的硝酸分别浸泡未包覆的镍钴锰酸锂三元正极活性材料（NCM）和包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料（NCM-Al2O3）30min后固液混合物液相中各种金属离子的浓度；表2所示，表示0.03m/L的盐酸分别浸泡未包覆的镍钴锰酸锂三元正极活性材料（NCM）和包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料（NCM-Al2O3）30min后固液混合物液相中各种金属离子的浓度；表3所示，表示0.03m/L的醋酸分别浸泡未包覆的镍钴锰酸锂三元正极活性材料（NCM）和包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料（NCM-Al2O3）30min后固液混合物液相中各种金属离子的浓度。可见，在同等条件下未包覆的镍钴锰酸锂三元正极活性材料与包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料同一时间溶出的金属离子浓度不同，且同一时间包覆有三氧化二铝的镍钴锰酸锂三元正极活性材料的金属离子浓度小于未包覆的镍钴锰酸锂三元正极活性材料的金属离子浓度。由此可见，包覆效果可以体现在固液混合物中液相的金属离子浓度上，即，通过固液混合物液相中金属离子浓度变化可以反映正极活性材料的表面包覆效果。
表1
Figure WO236-appb-I000001
表2
Figure WO236-appb-I000002
表3
Figure WO236-appb-I000003
实施例1
本实施例中酸溶液为醋酸溶液。
称取0.4gNaOH溶解于100ml去离子水中，定容稀释至1000ml，称取2.04g邻苯二甲酸氢钾加水溶解，用所述NaOH溶液滴定该邻苯二甲酸氢钾溶液；用已标定的NaOH溶液进行滴定所述醋酸溶液测得实际醋酸浓度；称取10g包覆质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料于三口烧瓶中，量取100ml实际浓度为0.03mol/L的醋酸溶液加入上述三口烧瓶中浸泡所述镍钴锰酸锂，在该三口烧瓶插入PH计探头及温度计且密封，水浴25°C加热并匀速搅拌所述固液混合物， 120min后量取一次该固液混合物，采用火焰原子吸收测得该固液混合物中金属离子的浓度大小，即待测金属离子浓度1；之后，称取10g通过扫描电镜观察认为包覆效果好且包覆有质量比1%三氧化二铝的镍钴锰酸锂三元正极活性材料，进行上述同样的实验过程，并120min后量取一次该固液混合物，采用火焰原子吸收测得该固液混合物中金属离子的浓度，即标准金属离子浓度，比较所述待测金属离子浓度大小与标准金属离子浓度大小。
实施例2
与实施例1的区别为称取10g采用不同工艺包覆有质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料，记录固液混合溶液中的金属离子浓度为待测金属离子浓度2，比较该待测待测金属离子浓度2与标准金属离子浓度大小。
分别测量实施例1中待测金属离子浓度1、实施例2中待测金属离子浓度2及标准金属离子浓度，测量数据如下表所示：
Figure WO236-appb-I000004
通过上述各种金属离子浓度数据可以得知，同样10g包覆有质量比为1%三氧化二铝的镍钴锰酸锂三元正极活性材料包覆效果不同引起固液混合物液相中金属离子浓度不同。实施例1中Li离子浓度、Ni离子浓度、Co离子浓度、Mn离子浓度分别比对应的标准金属离子浓度大，则判断实施例1中三氧化二铝的包覆效果比标准的三氧化二铝包覆效果差；实施例2中Li离子浓度、Ni离子浓度、Co离子浓度、Mn离子浓度分别比对应的标准金属离子浓度小，则判断实施例2中三氧化二铝的包覆效果比标准的三氧化二铝包覆效果好。
本发明正极活性材料表面包覆效果的检测方法根据酸溶液与包覆正极活性材料反应后溶液的pH值或反应后溶液中各种金属离子浓度来检测正极活性材料表面的包覆效果，该检测方法成本低、简单有效，能够满足生产及科研工作的需要，可以用于样品表面包覆效果的检测。
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。

Claims (10)

  1. 一种正极活性材料表面包覆效果的检测方法，包括：
    S1，提供一预定浓度的酸溶液；
    S2，将待测的包覆正极活性材料放置于一容器；
    S3，将所述酸溶液加入所述容器直至完全浸泡该待测的包覆正极活性材料，形成一第一固液混合物；
    S4，密封上述容器，加热并搅拌所述第一固液混合物，同时记录不同时间所述第一固液混合物中液相的pH值，即待测pH值；以及
    S5，通过比较所述待测pH值与标准pH值判断该待测的包覆正极活性材
    料的表面包覆效果。
  2. 如权利要求1所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，所述酸溶液的浓度范围为0.01 mol/L～0.5mol/L。
  3. 如权利要求1所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，所述待测的包覆正极活性材料与预定浓度的酸溶液的固液比范围为1：1000～1：1，该固液比是指待测的包覆正极活性材料质量与酸溶液体积的比例。
  4. 如权利要求1所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，使加热并搅拌过程中温度保持恒定。
  5. 如权利要求1所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，所述标准pH值确定方法如下：
    S51，提供所述预定浓度的酸溶液；
    S52，将标准的包覆正极活性材料放置于一容器；
    S53，将所述酸溶液加入所述容器直至完全浸泡该标准的包覆正极活性材料，形成一第二固液混合物；以及
    S54，密封上述容器，加热并搅拌所述第二固液混合物，同时记录不同时间所述第二固液混合物中液相的pH值，即标准pH值。
  6. 如权利要求5所示的一种正极活性材料表面包覆效果的检测方法，其特征在于，该标准的包覆正极活性材料为具有合格的包覆效果的包覆正极活性材料。
  7. 如权利要求1所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，所述比较所述待测pH值与标准pH值判断待测的包覆正极活性材料的表面包覆效果的步骤可进一步包括：
    当待测pH最大值小于标准pH最大值时，则判断待测的包覆正极活性材料中金属离子的溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差；或
    当同一时刻待测pH值小于标准pH值时，则判断该待测的包覆正极活性材料中金属离子的溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差；又或
    当检测过程中待测pH值变化速率小于标准pH值变化速率时，则判断该待测的正极活性材料与酸溶液反应速度较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差。
  8. 一种正极活性材料表面包覆效果的检测方法，包括：
    S1，提供一预定浓度的酸溶液；
    S2，将待测的包覆正极活性材料放置于一容器；
    S3，将所述酸溶液加入所述容器直至完全浸泡该待测的包覆正极活性材料，形成一第三固液混合物；
    S4，密封上述容器，加热并搅拌所述第三固液混合物，同时记录不同时间所述第三固液混合物液相中各种金属离子的浓度，即待测金属离子浓度；以及
    S5，通过比较所述待测金属离子浓度与标准金属离子浓度判断待测的包覆正极活性材料的表面包覆效果。
  9. 如权利要求8所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，所述标准金属离子浓度的确定方法如下：
    S51，提供所述预定浓度的酸溶液；
    S52，将标准的包覆正极活性材料放置于一容器；
    S53，将所述酸溶液加入所述容器直至完全浸泡所述标准的包覆正极活性材料，形成一第四固液混合物；以及
    S54，密封上述容器，加热并搅拌所述第四固液混合物，同时记录不同时间所述第四固液混合物液相中各种金属离子浓度，即标准金属离子浓度。
  10. 如权利要求8所述的一种正极活性材料表面包覆效果的检测方法，其特征在于，比较所述待测金属离子浓度与标准金属离子浓度判断待测的包覆正极活性材料的表面包覆效果的步骤进一步包括:
    当待测金属离子浓度的最大值小于标准金属离子浓度的最大值时，则判断待测的包覆正极活性材料中金属离子溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差；或
    当同一时刻待测金属离子浓度小于标准金属离子浓度时，则判断该待测的包覆正极活性材料中金属离子溶出速率较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差；又或
    当检测过程中待测金属离子浓度的变化速率小于标准金属离子浓度的变化速率时，则判断该待测的正极活性材料与酸溶液反应速度较慢，该待测的包覆正极活性材料包覆效果好，反之则包覆效果差。
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