CN111380996A - Rapid detection method for cycle life of anode material - Google Patents
Rapid detection method for cycle life of anode material Download PDFInfo
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- CN111380996A CN111380996A CN201811638352.4A CN201811638352A CN111380996A CN 111380996 A CN111380996 A CN 111380996A CN 201811638352 A CN201811638352 A CN 201811638352A CN 111380996 A CN111380996 A CN 111380996A
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- positive electrode
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- cycle life
- acidic solution
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- 238000001514 detection method Methods 0.000 title claims abstract description 38
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- 238000000034 method Methods 0.000 claims abstract description 71
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/20—Metals
- G01N33/202—Constituents thereof
- G01N33/2028—Metallic constituents
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
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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]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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Abstract
The invention relates to a rapid detection method for cycle life of a positive electrode material. In particular, the invention relates to LiFePO4The rapid detection method for the cycle life of the anode material comprises the following steps: (1) reacting said LiFePO4Mixing the powder of the anode material with an acidic solution to react; (2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances; (3) detecting the concentration C of the metallic element Fe in the filtrateFeAnd according to the concentration C of the metallic element FeFeEvaluating the LiFePO4Cycle life of the positive electrode material. By adopting the method, different LiFePO can be rapidly detected and compared4Metal elution property of positive electrode materialThereby rapidly predicting the cycle life of the cathode material and the cycle life of a battery cell or a battery obtained from the cathode material. The process of the invention is particularly useful for LiFePO4Life evaluation and long life LiFePO of positive electrode material4Selection of the anode material.
Description
Technical Field
The invention relates to the field of lithium ion battery materials. In particular, the invention relates to a rapid detection method for cycle life of a positive electrode material. The invention also relates to a rapid comparison method for the cycle life of the anode material.
Background
As a high-efficiency energy storage and conversion device, the lithium ion secondary battery has significant advantages in energy density, cycle life, environmental friendliness, and the like, compared to conventional nickel-based batteries, lead-acid batteries, and the like. The material properties of the positive electrode material, which is used as a key component of the lithium ion secondary battery, can directly determine the performance and service life of the battery core. For example, LiFePO is used4The lithium ion battery which is a positive electrode material is widely applied to urban public transport power systems due to the characteristics of long cycle life, high safety performance, low cost and the like, and has important application prospects in the field of large-scale energy storage.
However, due to the difference of raw materials and synthesis processes adopted by different manufacturers of the cathode material, the synthesized cathode material shows obvious differences in physical and chemical properties in the aspects of crystallinity, particle size distribution, specific surface, impurity content, carbon-coated property and the like, and further influences the dissolution property of metal elements in the cathode material and the life decay behavior of a battery core manufactured by the cathode material. LiFePO is associated with factors such as electrolyte composition, purity, and cell design4The metal elution property and the attenuation behavior of the positive electrode material are comprehensively affected by factors such as the crystallinity, the carbon coating uniformity and thickness, the content of impurity components, and the particle size distribution, among others, of the positive electrode material itself.
Since the difference of the anode material powder is small, how to rapidly detect the cycle life of the anode material so as to perform screening is a technical problem in the field. The conventional detection means, such as SEM and XRD, have high detection limits, and thus the positive electrode materials cannot be distinguished in detail. And more precise testing means such as HRTEM, XPS, Raman and the like have higher testing cost, complex sample preparation process and higher operation technical requirement. In another method, the positive electrode material is made into a cell for test evaluation. Although the method can intuitively display the actual performance of the material in the battery cell, the method has the defects of longer battery cell manufacturing period, higher raw material cost, higher test cost, higher labor cost and the like. In addition, it has been reported that the quality of a battery pole piece can be judged by measuring the glossiness of the battery pole piece. However, the method has a small application range, cannot truly reflect the overall performance of the cathode material, and has low accuracy.
Therefore, there is a need for a positive electrode material (especially LiFePO)4Cathode material), which is suitable for an actual production process and can quickly and accurately detect or compare the metal dissolution properties of the cathode material, thereby quickly predicting the cycle life of the cathode material and the cycle life of a battery cell or battery obtained from the cathode material.
Disclosure of Invention
With the technical solution described herein, the above object can be achieved.
A first aspect of the present invention provides a LiFePO4The rapid detection method for the cycle life of the anode material comprises the following steps:
(1) reacting said LiFePO4Mixing the powder of the anode material with an acidic solution to react;
(2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances;
(3) detecting the concentration C of the metallic element Fe in the filtrateFeAnd according to C of said metallic element FeFeConcentration evaluation of the LiFePO4Cycle life of the positive electrode material;
wherein the initial concentration C of the acidic solutionAcid(s)In the range of 0.002mol/L to 1mol/L, preferably in the range of 0.01mol/L to 1mol/L, and the Q value of the process satisfies Q.ltoreq.92%, preferably Q.ltoreq.90%, the Q value being defined as Q ═ C (n ≦ CFe)/(1000*Ar*CAcid(s)*η)*100％，
N＝2；
CFeRepresents the concentration of the metallic element Fe in the filtrate in ppm;
ar represents the relative atomic mass of the metallic element Fe;
Cacid(s)Representing the initial concentration of the acidic solution, expressed in mol/L;
η denotes H ionized by a single acid molecule in the acidic solution+And (4) counting.
A second aspect of the present invention provides a LiFePO4The rapid detection method for the cycle life of the anode material comprises the following steps:
(1) reacting said LiFePO4Mixing powder of the positive electrode material with an acidic solution having an initial concentration C to perform a reactionAcid(s)In the range of 0.002mol/L to 1mol/L, preferably in the range of 0.01mol/L to 1 mol/L;
(2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances;
(3) detecting the concentration C of the metallic element Fe in the filtrateFeAnd calculating a Q value, wherein Q is as defined above;
(4) if the calculated Q value satisfies Q.ltoreq.92% (preferably, Q.ltoreq.90%), according to the concentration C of the metallic element FeFeEvaluating the LiFePO4Cycle life of the positive electrode material; otherwise, adjusting one or more conditions selected from the group consisting of the amount of the positive electrode material powder, the volume and concentration of the acidic solution, the kind of the acid, the reaction temperature and the time, and repeating the above steps (1) to (3) until the Q value meets the above requirements.
A third aspect of the invention provides a method for the production of a plurality of LiFePO4The method for rapidly comparing the cycle life of the anode material comprises the following steps:
according to the rapid detection method of the first aspect of the present invention, the LiFePO is separately detected4Detecting the positive electrode material with the same test parameters, and comparing the concentration C of the metal element Fe in the filtrateFeThereby to a plurality of said LiFePO4Positive electrode materialThe cycle life of the materials was compared.
By adopting the method, different LiFePO can be rapidly detected and compared4The metal dissolution property (particularly the iron dissolution property) of the cathode material, so that the LiFePO can be rapidly predicted4Cycle life of positive electrode material and lithium iron phosphate (LiFePO)4Cycle life of the cell or battery obtained from the positive electrode material.
Drawings
FIG. 1 shows a typical LiFePO4Attenuation curve of the cell.
FIG. 2 shows different LiFePO4The material is matched with a cycle attenuation curve of a graphite I full cell at 45 ℃.
FIG. 3 shows different LiFePO4The material is matched with a cycle attenuation curve of a graphite II full cell at 25 ℃.
Detailed Description
It should be understood that the recitation of numerical ranges herein using endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
All numerical values provided herein are to be considered as modified by the term "about" unless otherwise indicated herein or otherwise clearly contradicted by context. Also, the term "about" as used herein is understood to be within the normal tolerance of the art, e.g., including values up to 10% higher and up to 10% lower, preferably up to 5% higher and up to 5% lower, than the recited value or range.
Hereinafter, various exemplary embodiments according to the present invention are described in detail.
The invention provides a method for rapidly detecting the cycle life of a positive electrode material. The method can be used for rapidly detecting the metal dissolution property of the anode materials such as lithium ion batteries and the like, rapidly screens different materials from the material powder level, and provides a technical basis for screening the anode materials of long-life battery cores.
A particularly suitable cathode material for the process of the first aspect of the invention is LiFePO for lithium ion batteries4And (3) a positive electrode material. In the present application, the term "LiFePO4By "positive electrode material" is meant that the positive electrode material comprises pure LiFePO4(lithium iron phosphate, or LFP for short) or essentially pure LiFePO4And (4) forming. Typically, the LiFePO4The positive electrode material comprises at least 50 wt% (i.e. weight percent) pure LiFePO4Preferably at least 60 wt%, more preferably at least 70 wt%, most preferably at least 80 wt% pure LiFePO4. In particular, pure LiFePO4For example, it may comprise at least 85 wt%, more preferably at least 90 wt%, even more preferably at least 92 wt%, such as 95 wt% or 99 wt% of the total weight of the positive electrode material. The LiFePO4The anode material contains pure LiFePO4Besides, other common cathode materials of the lithium battery, such as lithium cobaltate, lithium manganate, nickel-cobalt-aluminum ternary materials, nickel-cobalt-manganese ternary materials and the like, can be contained, and/or other conventional additives can be contained.
The principles of the present invention are explained below. However, it should be understood by those skilled in the art that the theoretical explanations provided herein are merely the most likely correct explanations based on the present knowledge of the inventor and the state of the art, which are intended to facilitate an understanding of the present invention. With the development of science and technology, these theoretical explanations may prove to be not completely correct. Therefore, the present invention is not limited by these theoretical explanations.
FIG. 1 shows a typical LiFePO4Attenuation curve of the cell. In fig. 1, the end of life is defined as the decay of the cell capacity to 80% of the initial capacity. The trend II shows the ideal decay curve, and the trend I shows the LiFePO in practical use4Attenuation curve of the cell. Stage 1 and stage 2 are generally considered to be different LiFePO4Common decay phase of cells, the rapid decay of phase 1 capacity due toRapid repair and reformation of post-formation negative electrode SEI (solid electrolyte interface film); entering a stage 2, the repair of the SEI tends to be stable, and the attenuation tends to be slow; and different LiFePO4The cells may exhibit different decay tendencies at stage 3. When the amount of electrolyte in the battery cell is sufficient, the capacity of the phase 3 trend II is accelerated to appear a fading inflection point, which is mainly caused by the fact that the impedance of the battery cell is suddenly increased due to the accelerated consumption of the anode active lithium and the thickening of the SEI film, so that the amount of lithium ions which can be cyclically extracted is rapidly reduced. Theoretical research and practice show that during the cell cycle, the anode LiFePO4The iron in the electrolyte can be continuously and slowly dissolved out to form solvated Fe2+And when charged, will pass through the separator to reach the negative electrode and reduce and deposit on the negative electrode. The deposited reduction products of iron may occupy lithium intercalation active sites on the surface of the negative electrode, preventing the normal deintercalation of active lithium. More seriously, the reduction products of the iron can damage the SEI film of the negative electrode and promote the repair cycle of the damaged SEI. When the amount of iron deposited reaches a certain limit, it can cause qualitative changes in the cell decay behavior, directly resulting in accelerated consumption of active lithium and a sudden increase in the cell impedance. Thus, LiFePO4The iron leaching mechanism is one of the most important reasons for accelerating the attenuation of the cell in the later period of the cycle.
Although LiFePO4The dissolution of the intermediate iron is a complex process, but without wishing to be bound by theory, it is believed that: with LiFePO4For example, in a cell environment, LiPF is accelerated by trace amounts of water in the electrolyte6Decomposition to HF, H formed+With LiFePO4Fe in (1)2+Exchange reaction occurs to make Fe2+Dissolving out into the electrolyte and generating side reaction, which affects the performance of the battery cell. The schematic reaction equation for LFP with an acidic solution is:
LiFePO4+H+→Fe2++Li++HPO4 2-+H2PO4 -+H3PO4(formula 1-1).
Therefore, the service life of the cathode material can be predicted by simulating the acceleration process of corrosion of the LFP cathode material by HF in the battery cycle process and monitoring the dissolved metal Fe. Therefore, the service life of the anode material can be visually judged without preparing a secondary battery, the verification period of raw materials in the production process is saved, and the cost is reduced.
Thus, in some embodiments, the method of the invention comprises the steps of:
(1) reacting said LiFePO4Mixing the powder of the anode material with an acidic solution to react;
(2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances;
(3) detecting LiFePO-derived in the filtrate4The concentration of the metal element Fe of the positive electrode material, and the cycle life of the positive electrode material is evaluated according to the concentration of the metal element Fe.
In this method, the cycle life of the positive electrode material to be measured is evaluated and predicted using the concentration of the eluted metal element Fe as an index. The key and difficulty of the method for achieving success lies in how to select a proper acid environment and reaction parameters and control the corrosion degree of the acid solution on the anode material so as to more accurately simulate the corrosion process of HF on the anode material.
The inventors have surprisingly found that in order to be able to detect LiFePO quickly and accurately4According to the technical scheme of the invention, the specific selection of the conditions such as the quality of the anode material to be measured, the concentration and volume of an acidic solution, the type of acid, the reaction temperature and time can ensure that the pH change (delta pH) of a reaction solution before and after reaction is as small as possible, and the reaction of the anode material is controlled in a proper range, so that the cycle life of the anode material can be more accurately predicted according to the concentration of dissolved out metal element Fe.
For this purpose, the process of the invention requires an initial concentration of the acidic solution and H in the course of the reaction+The amount of consumption is severely limited.
In addition, for the accuracy of the measurement, the initial concentration of the acidic solution should be in the range of 0.002 to 1mol/L, preferably the initial concentration of the acidic solution is in the range of 0.005 to 1mol/L, more preferably in the range of 0.01 to 1mol/L, even more preferablyAnd is in the range of 0.05mol/L to 1 mol/L. For example, the initial concentration of the acidic solution can be from 0.002mol/L, 0.005mol/L, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.05mol/L, or 0.1mol/L to 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, or 1 mol/L. In an exemplary embodiment, the initial concentration of the acidic solution is in the range of 0.01mol/L to 1 mol/L. If the concentration is too low, the acid consumption is too fast at the beginning of the reaction, so that the acid amount in the process is insufficient; if the concentration is too high, LiFePO is added4The positive electrode material is dissolved quickly, and the acid resistance of the positive electrode material and the dissolution rate of the metal element Fe cannot be truly reflected.
Also, the inventors have found that in the method of the present invention, H+Is another key parameter that affects the accuracy of the method. By controlling H+Consumption or H+The relative consumption of the reaction solution is controlled to control the pH change of the reaction solution before and after the reaction. H+Consumption or H+The smaller the relative consumption of delta pH; and vice versa. The inventors have surprisingly found that by reacting H in an acidic solution+Consumption or H+The relative consumption of (a) is controlled within a suitable range, the degree of reaction can be controlled very well, so that the reaction is fast and the error of the method of the invention is small. In particular, H+The consumption must not be too great or too small. H+When the amount of consumption is too small, the degree of reaction is too sufficient, and LFP may be completely consumed or the acid may be too weak to start the reaction, resulting in a large error. H+If the consumption amount is too large, the error is large because the loss threshold of the acid is close to the threshold, and the LFP can still react but the acid is not present.
In the method of the present invention, H can be characterized by Q value+Relative consumption of (c). The Q value is defined as Q ═ (n ═ C)Fe)/(1000*Ar*CAcid(s)η) 100% of the total weight of the composition, wherein
n is 2(n represents the same as the LiFePO)4H for each Fe atom in the positive electrode material to react+The number of (d);
CFerepresents the concentration of the metallic element Fe in the filtrate in ppm;
ar represents the relative atomic mass of the metallic element Fe;
Cacid(s)Representing the initial concentration of the acidic solution, expressed in mol/L;
η denotes H ionized by a single acid molecule in the acidic solution+And (4) counting.
In the process of the present invention, the Q value should be controlled to be Q.ltoreq.92% or preferably Q.ltoreq.90%. For example, the Q value may be about 6%, about 10%, about 15%, about 20%, about 30%, about 50%, about 60%, about 70%, about 80%, or about 85%. When the Q value is within these preferred ranges, H is indicated+The relative consumption of the metal element Fe is proper, the delta pH before and after the reaction is small, the dissolution reaction of the metal element Fe can reach a reasonable degree in a short time, and the dissolution degree of the metal element Fe can be used for representing the acid resistance of the cathode material, so that the cycle life of the cathode material can be accurately predicted or estimated based on the dissolution degree of the metal element Fe.
The value of n in the above formula represents LiFePO4Cathode material for H in acid solution+The proportion of consumption of (c). For LiFePO4In the case of Fe in divalent form Fe (II), 2 parts of H are consumed per part of Fe+So n is 2. Thus, for LiFePO4The positive electrode material may also have a Q value defined as Q ═ (2 ═ C)Fe)/(1000*Ar*c[H+]*η)*100％。
In some embodiments, the powder of the positive electrode material has a mass of 0.2g to 10 g. Preferably, the mass of the powder is 0.3g to 8g, more preferably 0.5g to 5.0 g. For example, the powder has a mass of 0.4g, 0.6g, 0.8g, 1.0g, 1.2g, 1.5g, 2.0g, 2.5g, 3.0g, 3.5g, 4.0g, or 4.5 g.
In some embodiments, an aqueous solution of a strong inorganic acid is used as the acidic solution. The strong inorganic acids commonly used are well known in the art. In the context of the present invention, "strong acid" refers to an acid having a pKa in water of less than 3, preferably a pKa of less than 2, more preferably a pKa of less than 1. Some examples of strong inorganic acids include HCl, HF, HNO3、H2SO4And H3PO4And the like, as well as any combination thereof. In some preferred embodimentsIn one embodiment, the acidic solution comprises HCl, HF, HNO3、H2SO4And H3PO4Any one or more of the group consisting of. More preferably, HCl, HF, H are used2SO4Or any combination thereof. Most preferably, HCl or H is used2SO4。
In some embodiments, the volume of the acidic solution is in the range of 30ml to 2000 ml. Preferably, the volume of the acidic solution is in the range of 50ml to 1500ml, more preferably in the range of 80ml to 1200ml, even more preferably in the range of 100ml to 1000 ml. For example, the volume of the acidic solution may be 200ml, 300ml, 400ml, 500ml, 600ml, 700ml, 800ml or 900 ml.
Without wishing to be bound by theory, generally, higher temperatures favor the dissolution of the metallic element Fe because side reactions are exacerbated at high temperatures and the decay of the positive electrode material is accelerated so that the "knee" of the capacity accelerated decay occurs earlier. However, too high temperature may cause too fast evaporation of the solution and loss of acid molecules in the acidic solution, thereby affecting the accuracy of the detection result. Thus, it is desirable to control the reaction temperature within a suitable range, both to carry out the reaction relatively quickly and without affecting the accuracy of the results.
In some embodiments, the reaction of step (1) is carried out at a temperature of 5 ℃ to 65 ℃. Preferably, the reaction of step (1) is carried out at a temperature of from 10 ℃ to 60 ℃, more preferably from 15 ℃ to 55 ℃. For example, the reaction of step (1) is carried out at a temperature of 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 60 ℃.
In some embodiments, the reaction of step (1) is carried out for 2 minutes to 120 minutes. Preferably, the reaction of step (1) is carried out for 3 to 90 minutes, more preferably for 5 to 60 minutes. For example, the reaction of step (1) is carried out at a temperature of 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, or 60 minutes.
The amount of the powder of the positive electrode material, the selection of the acid, the volume and the concentration of the acidic solution, and the like in step (1) are not particularly limited. The preferred modes provided above are merely exemplary preferred technical solutions, not restrictive, in order to simultaneously rapidly and accurately detect the cycle life of the positive electrode material in a small scale experiment. Based on the content described in the present specification and the independent claims, those skilled in the art can determine the amount of powder of the suitable positive electrode material, the selection of the acid, the volume and the concentration of the acidic solution according to the actual requirements, so as to quickly detect or compare the cycle life of the positive electrode material. Therefore, based on the description herein, one skilled in the art would consider scaling up or down each parameter system, for example, scaling up or down the amount of powder, the volume of the acidic solution, etc., to achieve equivalent results.
In step (2) of the process of the present invention, the mixture can be rapidly separated using solid-liquid separation methods known in the art to obtain a filtrate and insoluble matter. Common solid-liquid separation methods include centrifugation, normal pressure filtration, reduced pressure filtration, and the like. For example, high speed centrifugation or a microporous needle filter membrane may be used for the separation.
In the method of the present invention, the step (3) may be performed by a method of detecting the concentration of a metal element in a solution known in the art. For example, the detection in step (3) is one or more of ICP, uv spectroscopy, electrochemical method, atomic absorption method, or atomic emission method. Concentration C of metallic element FeFeIs defined as CFe(mass of detected metal element Fe)/(total mass of detected solution). Due to the concentration CFeTypically lower and for convenience are usually in ppm (parts per million) units.
The concentration of the metallic element Fe obtained in step (3) reflects the amount of the metallic element Fe dissolved out of the positive electrode material during the reaction. Under the same parameters and reaction conditions, for the same type of positive electrode material (for example for LiFePO)4Positive electrode material), concentration C of metallic element FeFeThe higher the metal Fe is, the more Fe is dissolved out, which indicates that the cycle life of the cathode material is shorter; and vice versa.
Therefore, the concentration of the metallic element Fe measured in step (3) can be used as an evaluation LiFePO4Circulation of positive electrode active materialAn indication of lifetime. According to the concentration of the metal element Fe, the catalyst can be applied to LiFePO4The cycle life of the positive electrode active material was evaluated qualitatively or quantitatively.
For qualitative evaluation, for example, LiFePO with a known cycle life can be used4The positive electrode material was performed as a standard reference. Specifically, the concentration C of the metal element Fe obtained by the standard reference object under the reference parameters and conditions is determined by selecting suitable experimental parameters and conditions as the reference parameters and conditions through experimentsFe standardWhile ensuring that Q is within the preferred ranges defined above. When a certain LiFePO needs to be quickly determined4During the cycle life of the anode material, the LiFePO to be measured is subjected to parameter and condition serving as reference4Detecting the concentration of the metallic element Fe in the anode material to obtain the concentration C of the metallic element FeFe testWhile ensuring that Q is within the preferred ranges defined above. C is to beFe standardAnd CFe testComparing the measured values to quickly evaluate the LiFePO to be measured4Cycle life of the positive electrode material. Specifically, if CFe standard>CFe testLiFePO as standard reference4The cycle life of the anode material is shorter than that of the anode material tested; if C is presentFe standard<CFe testLiFePO as standard reference4The cycle life of the positive electrode material was longer than that of the tested positive electrode material.
For quantitative evaluation, for example, a series of LiFePO's with different cycle lives may be used4The positive electrode material served as a standard reference. Specifically, the concentration C of the metal element Fe obtained by the series of standard reference substances under the reference parameters and conditions is determined by selecting suitable experimental parameters and conditions as the reference parameters and conditions through experimentsFe standardWhile ensuring that Q is within the preferred ranges defined above. Meanwhile, standard batteries were prepared for the series of standard reference substances, and their cycle lives were measured under standard conditions, respectively. Then, the concentration C of Fe for each metal element was determined in accordance with the cycle life of each reference materialFe standardPlotted and curve fitted. Quickly determine when neededCertain LiFePO4During the cycle life of the anode material, the LiFePO to be measured is subjected to parameter and condition serving as reference4Detecting the concentration of the metallic element Fe in the anode material to obtain the concentration C of the metallic element FeFe testWhile ensuring that Q is within the preferred ranges defined above. Then based on the measured CFe testThe cycle life of the material can be quickly estimated by using the fitted curve.
Those skilled in the art will understand that: various limitations on the technical features and various preferred ranges given for the parameters in the different embodiments of the invention mentioned above can be combined arbitrarily, and the various embodiments obtained by combining the limitations and the preferred ranges are still within the technical scope of the invention claimed and are considered as part of the disclosure of the present specification.
The second aspect of the invention also provides LiFePO4The rapid detection method for the cycle life of the anode material comprises the following steps:
(1) reacting said LiFePO4Mixing powder of the positive electrode material with an acidic solution having an initial concentration C to perform a reactionAcid(s)In the range of 0.002mol/L to 1mol/L, preferably in the range of 0.01mol/L to 1 mol/L;
(2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances;
(3) detecting the concentration C of the metallic element Fe in the filtrateFeAnd calculating the Q value (wherein Q is as defined above);
(4) if the calculated Q value satisfies Q.ltoreq.92% (preferably, Q.ltoreq.90%), according to the concentration C of the metallic element FeFeEvaluating the LiFePO4Cycle life of the positive electrode material; otherwise, adjusting one or more conditions selected from the group consisting of the amount of the positive electrode material powder, the volume and concentration of the acidic solution, the kind of the acid, the reaction temperature and the time, and repeating the above steps (1) to (3) until the Q value meets the above requirements.
Using the above method, for various LiFePO4The anode material can conveniently determine proper experimental conditions to ensure that the Q value falls in a proper regionThereby ensuring the accuracy of the detection result.
Those skilled in the art will appreciate that the calculation in step (3) and the judgment in step (4) may be performed by an experimental operator, or may be automatically performed by a computer program.
In another aspect of the invention, a method for preparing multiple LiFePO is provided4The method for rapidly comparing the cycle life of the anode material comprises the following steps:
according to the method described in the first aspect of the invention, the LiFePO is treated separately4Detecting the positive electrode material with the same test parameters, and comparing the concentration C of the metal element Fe in the filtrateFeThereby to a plurality of said LiFePO4The cycle life of the positive electrode materials was compared.
The same applies to the second and third aspects of the invention as described above for the first aspect of the invention (e.g. preferences and preferred ranges for the respective parameters).
The method can visually judge the service life of the anode material without preparing a secondary battery, save the verification period of raw materials in the production process and reduce the cost.
The method of the invention can be used for preparing lithium ion batteries. For ease of understanding, one example of a lithium ion battery is provided below. The lithium ion battery comprises a positive electrode, a negative electrode, an isolating membrane and electrolyte.
The positive electrode of the lithium ion battery comprises a positive electrode current collector and a positive electrode diaphragm arranged on the surface of the current collector. The negative electrode of the lithium ion battery comprises a negative electrode current collector and a negative electrode diaphragm arranged on the surface of the current collector.
The positive electrode diaphragm of the lithium ion battery comprises a positive electrode active material, a binder and a conductive agent. The anode active material is mainly LiFePO4The synthesis process includes, but is not limited to, carbothermic method, sol-gel method, hydrothermal synthesis method, spray pyrolysis method, liquid phase precipitation method, micro-emulsion method, microwave method, etc. The binder is preferably polyvinylidene fluoride (PVDF), polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene-propylene terpolymer and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymerOne or more of tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin. The conductive agent is preferably selected from one or more of conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nanotubes.
A negative electrode membrane of a lithium ion battery includes a negative electrode active material, a binder, and optionally a conductive agent. The negative active material is a material capable of accepting and extracting lithium ions, and preferably, can be selected from one or more of natural graphite, artificial graphite, soft carbon, hard carbon, silicon-oxygen compound and silicon-carbon compound. The adhesive is preferably selected from one or more of styrene-butadiene rubber emulsion (SBR), acrylic resin and acrylonitrile. The conductive agent is preferably selected from one or more of conductive carbon black, superconducting carbon black, conductive graphite, acetylene black, ketjen black, graphene and carbon nanotubes.
In the lithium ion battery described herein, the separator comprises any separator material used in existing lithium ion secondary batteries, preferably, selected from the group consisting of polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite films thereof.
In the lithium ion batteries described herein, the electrolyte comprises a lithium salt, an organic solvent, and optional additives. The lithium salt includes, but is not limited to, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, LiN (SO)2CnF2n+1)2And LiN (SO)2F)(SO2CnF2n+1) (n is an integer of 1-10), lithium hexafluoroarsenate, lithium tetrafluoro oxalate phosphate, bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium bis (oxalato) borate, and lithium difluoro oxalate borate, and preferably LiPF6. The organic solvent includes, but is not limited to, one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), methyl propyl carbonate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl propionate, ethyl butyrate, ethyl propionate, propyl butyrate, and one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, vinylene carbonate, ethylene sulfite, propylene sulfite, γ -butyrolactone, and tetrahydrofuran. The organic solvent may be singlyOne is used alone, or two or more can be mixed according to a certain proportion.
The present application is further illustrated below by reference to examples and comparative examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. Unless otherwise indicated, the reagents used hereinafter are all commercially available.
Examples
1. Test methods and Material sources
In each of the examples and comparative examples, unless otherwise indicated, the chemical starting materials used were all materials of commercial origin conventionally employed in the battery industry and the analytical field, and the physicochemical and performance parameters involved were measured by methods conventional in the art. Some specific raw materials and parameter testing methods are as follows.
1) Positive electrode material
The LFPI, LFPII, LFPIV and LFPIV used in the examples were purchased from different commercial suppliers and were distinguished by crystallinity, particle size distribution, specific surface area, impurity level and/or carbon inclusion properties.
2) Other battery materials of detection kit
3) ICP detection
ICP instrument model: ICAP 7200ICP-OES, produced by ThermoFisher technologies Inc. (Primary heating and Power Co.);
and (3) testing conditions are as follows: the sample needs to be liquid, and if solid particles are contained, acid is added for digestion, or the solid particles are removed by filtration. The range of the element to be detected is required to be within the range of the standard curve, and if the range is exceeded, the sample is required to be diluted.
The main operation procedures are as follows: 1. testing a standard curve; 2. diluting a sample to be detected; 3. testing the diluted sample; 4. and (6) calculating and processing the data to obtain the concentration of the element to be detected.
Example 1
(1) Accurately weighing five Li of LFPII, LFPIII, LFPII, LFPIV and LFPIV respectivelyFePO41.000g of powder is added into a 2000ml big beaker;
(2) putting a clean magnetic stirrer, accurately measuring 1000ml of HCl solution with the concentration of 0.1mol/L, adding the HCl solution into a big beaker, and timing at room temperature to start stirring reaction;
(3) timing for 5min, and rapidly filtering and separating reaction clear liquid by adopting a 0.22-micron microporous needle type filter membrane;
(4) the reaction clear liquid is sent to ICP within 2h, and the concentration of dissolved Fe element is detected.
Example 2
Five kinds of LiFePO4The procedure for the detection of the powder was the same as in example 1, except that an HCl concentration of 0.01mol/L was used.
Example 3
Five kinds of LiFePO4The procedure for the detection of the powder was as in example 1, except that a volume of 100ml of HCl was used.
Example 4
Five kinds of LiFePO4The procedure for the detection of the powder was the same as in example 1, except that the reaction temperature was 60 ℃.
Example 5
Five kinds of LiFePO4The procedure for the detection of the powder was the same as in example 1, except that the reaction time was 60 min.
Example 6
Five kinds of LiFePO4The procedure for examining the powder was the same as in example 1 except that the mass of the examined sample was 5.000 g.
Example 7
Five kinds of LiFePO4The procedure for examining the powder was the same as in example 1, except that the HCl concentration used was 0.05mol/L and the mass of the examined sample was 2.000 g.
Example 8
Five kinds of LiFePO4The procedure for the detection of the powder was the same as in example 1, except that the HCl concentration used was 0.05mol/L and the reaction time was 15 min.
Example 9
Five kinds of LiFePO4The powder was examined as in example 1, except that the HCl concentration used was 0.05mol/L and the reaction temperature was 45 ℃.
Example 10
Five kinds of LiFePO4The procedure for the detection of the powder was the same as in example 1, except that the mass of the sample to be detected was 2.000g and the volume of HCl used was 500 ml.
Example 11
Five kinds of LiFePO4The powder was tested in the same manner as in example 1 except that the mass of the test sample was 2.000g and the reaction time was 15 min.
Example 12
Five kinds of LiFePO4The powder was tested as in example 1, except that a volume of 500ml of HCl was used and the reaction temperature was 45 ℃.
Example 13
Five kinds of LiFePO4The powder detection process was the same as in example 1 except that the reaction time was 15min and the reaction temperature was 45 ℃.
Example 14
Five kinds of LiFePO4The powder was tested as in example 1, except that the acid used was H2SO4。
Example 15
Five kinds of LiFePO4The powder was tested as in example 1, except that the acid used was H2SO4The acid concentration was 0.05mol/L, the volume was 500ml, and the reaction temperature was 45 ℃.
Example 16
Five kinds of LiFePO4The powder was tested as in example 1, except that the acid used was H2SO4The acid concentration was 0.01mol/L, the mass of the test sample was 2.000g, and the reaction time was 15 min.
Comparative example 1
Five kinds of LiFePO4The powder was tested in the same manner as in example 1 except that HCl was used in a concentration of 0.01mol/L, the mass of the test sample was 5.000g, and the reaction time was 60 min.
Comparative example 2
Five kinds of LiFePO4The procedure for the detection of the powder was the same as in example 1, except that 3mol/L HCl was used in a volume of 100 ml.
For comparison, the test conditions of examples 1 to 16 and comparative examples 1 to 2 are summarized in Table 1.
TABLE 1 examination conditions of examples 1 to 16 and comparative examples 1 to 2
Example 17
Five kinds of positive electrode materials were respectively made into full cells, and the actual cycle performance of the cells was measured.
The preparation and test process of the full cell is as follows:
(1) preparation of positive plate
Mixing the five different LiFePO4Respectively mixing positive active substances LFPII, LFPIV and LFPIV (the gram volume is 144mAh/g) with a conductive agent acetylene black and a binder PVDF according to the weight ratio of 95:3:2, adding a solvent N-methyl pyrrolidone, fully and uniformly stirring to obtain positive slurry, then coating the positive slurry on two surfaces of a positive current collector aluminum foil, and then drying and cold-pressing to obtain the positive plate made of five materials.
(2) Preparation of negative plate
Mixing the negative active material artificial graphite I and the artificial graphite II (with the gram volume of 342mAh/g) with acetylene black as a conductive agent, SBR and CMC according to the weight ratio of 95:1.5:3.1:0.4, adding deionized water as a solvent, fully stirring and uniformly mixing to obtain negative slurry, coating the negative slurry on two surfaces of a negative current collector copper foil, and drying and cold pressing to obtain two graphite negative plates.
(3) Preparation of electrolyte
At water content<Mixing EC, PC and DMC according to the weight ratio of EC to PC to DMC of 3 to 3 in a glove box with 10ppm argon atmosphere to obtain a mixed organic solvent, and fully drying lithium salt LiPF6Dissolving in the mixed organic solvent, and stirring to obtain electrolyte solution containing LiPF6The concentration of (2) is 1 mol/L.
(4) Preparation of the separator
The polyethylene porous membrane is used as a separation membrane.
(5) Assembly of full cell
And respectively matching the five material positive plates with two negative plates, placing the isolating films and stacking the isolating films in sequence to enable the isolating films to be positioned between the positive and negative plates to play an isolating role, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the prepared electrolyte, and carrying out packaging, low-current formation, high-temperature aging and other steps to obtain the lithium ion full battery.
(6) Testing of full cell cycle performance
At 45 ℃, five full batteries prepared by matching with the artificial graphite I are firstly charged with a constant current of 1C (namely, the current value of which the theoretical capacity is completely discharged within 1 h) until the voltage is 3.65V, then charged with a constant voltage of 3.65V until the current is 0.05C, and after standing for 5min, the batteries are discharged with a constant current of 1C until the voltage is 2.5V, which is a charge-discharge cycle process, and the discharge capacity of the time is the discharge capacity of the first cycle. The full cell was subjected to a number of cycles of charge and discharge testing according to the above method, and the number of cycles when the discharge capacity decayed to 80% of the initial capacity was detected.
The 45 ℃ cyclic decay curve of a full cell with different LFP materials and graphite I is shown in figure 2.
To further illustrate the detection method provided by the invention for long-life LiFePO4The detectability of the material is that for five full batteries prepared by matching with the artificial graphite II, the cyclic test temperature is changed to 25 ℃, the same test method is adopted to carry out the cyclic charge and discharge test for many times, and the cycle times when the discharge capacity is attenuated to 80 percent of the initial capacity are detected. The 25 ℃ cyclic attenuation curve of the full cell with different LFP materials and graphite II is shown in figure 3.
(7) Detection of iron element deposition amount of EOL battery cell (battery cell capacity is attenuated to 80% of initial capacity) negative pole piece
And after the cell is tested to EOL circularly according to the method, disassembling the cell and taking out the negative pole piece. Randomly punching two small circular sheets (1540.25 mm) at regular intervals on the whole negative pole piece2) At least 5 replicates were guaranteed. Digesting the punched pole piece by a digestion method, carrying out ICP (inductively coupled plasma) detection on the content of iron element, and averaging the results of all parallel samples to be used as a negative electrodeAnd (4) depositing amount of iron element of the pole piece. The results are shown in table 2 and in fig. 2 and 3.
TABLE 2 test results of examples 1 to 17 and comparative examples 1 to 2
FIGS. 2 and 3 show five different LiFePO examples 174The anode materials were matched with the cyclic attenuation curves of two types of artificial graphite (2 parallel samples), respectively. As can be seen from the figure, the five LFP materials show significant differences in attenuation behavior. Wherein LFPIV and LFPIV exhibit abnormal decay acceleration inflection points in the middle and later cycle phases, resulting in an "early" cutoff of the cycle life, which behaves in the same manner as trend I shown in FIG. 1. When the deposition amount of the cathode iron is found by disassembling and testing the EOL battery cell, the deposition amount of the cathode iron of the LFPIV and LFPIV battery cells is remarkably abnormal and higher, and iron is dissolved out more obviously at high temperature, so that the side reaction is aggravated and the attenuation acceleration inflection point appears earlier at the high temperature. From the cycle life of each LFP material battery cell, the EOL cycle numbers of the battery cells are sequentially reduced from LFP I to LFP V, and the quantity of iron deposited on the negative electrode is sequentially increased corresponding to the EOL, so that the correlation is obvious. It can be seen that the dissolution of iron from the LFP material and the reductive deposition on the surface of the negative electrode are one of the important causes of the life decay of the cell.
Examples 1 to 16 and comparative examples 1 to 2 are provided for carrying out rapid detection of iron solubility on the five LFP materials according to the method provided by the present invention, and the test results are shown in table 2. From examples 1 to 16, it can be seen that the iron solubility of the five LFP materials according to the method of the present invention can be distinguished significantly, and the iron solubility is gradually enhanced from lfpi to lfpv, which is consistent with the experimental results determined in example 17. For LFP I and LFP II, the amounts of 138ppm and 150ppm of the negative electrode deposition Fe were obtained at 45 ℃ and 83ppm and 112ppm of the negative electrode deposition Fe were obtained at 25 ℃ in example 17, respectively. It can be seen that the cathode material using LFP I actually has a longer cycle life than the cathode material using LFP II. This result is also obtained with the process of the invention. In examples 1 to 16, of LFP IIron content in powder material CFeAll lower than LFP II powder iron dissolving amount CFeThus characterizing the difference in cycle life of the positive electrode materials of LFP I and LFP II.
Therefore, the method of the invention well predicts the metal dissolution behavior and the service life difference of the cathode material in the battery core.
Further, comparison of examples 1 to 16 with comparative examples 1 to 2 shows that the amount C of iron dissolved in the LFP powderFeThe method is obviously influenced by factors such as the using amount of the tested powder, the volume and concentration of the used acid, the reaction time, the temperature and the like. When the initial acid concentration is appropriate and the pH change of the reaction solution before and after the reaction is within an appropriate range (corresponding to the Q value range defined herein), the iron solubility of different LFP materials can be significantly distinguished, as in examples 1 to 16. On the one hand, when the Q value is too large, for example, when the test powder is used in a large amount, the acid concentration is low and the reaction time is long, H in each reaction system+The depletion is over. According to the formula 1-1, the iron dissolution amount of the corresponding powder is close to the theoretical iron dissolution amount due to the limitation of the H + concentration, so that the iron dissolution distinction of the five LFP materials is poor or even impossible to distinguish (see comparative example 1). On the other hand, when the initial acid concentration C is usedAcid(s)At too high, LFP dissolution was severe (see comparative example 2). It is understood from the theoretical calculation of equation 1-1 (about 3500ppm when the theoretical dissolution is complete), that the five LFP materials are nearly complete in dissolution and therefore their iron solubility is indistinguishable. When the initial acid concentration C is usedAcid(s)When the amount is too low (e.g., less than 0.002mol/L), H in each reaction system+Too low a content to dissolve iron or too long a reaction time is needed without meaning, and the life of LFP cannot be predicted from the iron dissolution result. By comparing the Q values and c of the respective examples and comparative examplesAcid(s)Therefore, the following steps are carried out: to ensure the reliability of the prediction, CAcid(s)Should be controlled in the range of 0.002mol/L to 1mol/L, preferably in the range of 0.01mol/L to 1mol/L, and the Q value of the method should be controlled in the range of Q.ltoreq.92%, preferably in the range of Q.ltoreq.90%.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. LiFePO4The rapid detection method for the cycle life of the anode material comprises the following steps:
(1) reacting said LiFePO4Mixing the powder of the anode material with an acidic solution to react;
(2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances;
(3) detecting the concentration C of the metallic element Fe in the filtrateFeAnd according to the concentration C of the metallic element FeFeEvaluating the LiFePO4Cycle life of the positive electrode material;
wherein the initial concentration C of the acidic solutionAcid(s)In the range of 0.002mol/L to 1mol/L, preferably in the range of 0.01mol/L to 1mol/L, and the Q value of the process satisfies Q.ltoreq.92%, preferably Q.ltoreq.90%, the Q value being Q ═ C (n ^ C)Fe)/(1000*Ar*CAcid(s)*η)*100％，
n＝2；
CFeRepresents the concentration of the metallic element Fe in the filtrate in ppm;
ar represents the relative atomic mass of the metallic element Fe;
Cacid(s)Representing the initial concentration of the acidic solution, expressed in mol/L;
η denotes H ionized by a single acid molecule in the acidic solution+And (4) counting.
2. The rapid detection method according to claim 1, wherein the LiFePO4The anode material at least contains more than 50 wt% of pure LiFePO4Preferably, said pure LiFePO4In the LiFePO4The mass fraction in the positive electrode material is 60 wt% or more, and more preferably 70 wt%.
3. The rapid detection method according to claim 1, wherein the LiFePO4The mass of the powder of the positive electrode material is 0.2g to 10g, preferably 0.5g to 5.0 g.
4. The rapid detection method according to claim 1, wherein the volume of the acidic solution is 30ml to 2000ml, preferably 100ml to 1000 ml.
5. The rapid detection method according to any one of claims 1 to 4, wherein the acidic solution contains HCl, HF, HNO3、H2SO4And H3PO4One or more of (a).
6. The rapid detection method according to any one of claims 1 to 4, wherein the reaction is carried out at a temperature of 5 ℃ to 65 ℃, preferably at a temperature of 10 ℃ to 60 ℃,
and/or the reaction time is 2min to 120min, preferably the reaction time is 5min to 60 min.
7. The rapid detection method according to any one of claims 1 to 4, wherein in the step (2), the solid-liquid separation comprises one or more of centrifugation, normal pressure filtration, pressure filtration or reduced pressure filtration.
8. The rapid detection method according to any one of claims 1 to 4, wherein in the step (3), the detection is one or more of ICP, ultraviolet spectroscopy, electrochemistry, atomic absorption, or atomic emission.
9. For a plurality of LiFePO4The rapid comparison method for the cycle life of the anode material comprises the following steps: the method according to any one of claims 1 to 8, wherein the LiFePO is treated separately4A positive electrode material anddetecting the same test parameters, and comparing the concentration C of the metal element Fe in the filtrateFeThereby to a plurality of said LiFePO4The cycle life of the positive electrode materials was compared.
10. LiFePO4The rapid detection method for the cycle life of the anode material comprises the following steps:
(1) reacting said LiFePO4Mixing powder of the positive electrode material with an acidic solution having an initial concentration C to perform a reactionAcid(s)In the range of 0.002mol/L to 1mol/L, preferably in the range of 0.01mol/L to 1 mol/L;
(2) carrying out solid-liquid separation on the reaction mixture to obtain filtrate and insoluble substances;
(3) detecting the concentration C of the metallic element Fe in the filtrateFeAnd calculating Q ═ C (n ═ C)Fe)/(1000*Ar*CAcid(s)η) 100% of the total weight of the composition, wherein
n＝2，
CFeExpressed as the concentration of the metallic element Fe in the filtrate, expressed in ppm,
ar represents the relative atomic mass of the metal element Fe,
Cacid(s)Representing the initial concentration of the acidic solution, expressed in mol/L,
η denotes H ionized by a single acid molecule in the acidic solution+Counting;
(4) if the calculated Q value satisfies Q.ltoreq.92% (preferably, Q.ltoreq.90%), according to the concentration C of the metallic element FeFeEvaluating the cycle life of the positive electrode material; otherwise, adjusting one or more conditions selected from the group consisting of the amount of the positive electrode material powder, the volume and concentration of the acidic solution, the kind of the acid, the reaction temperature and the time, and repeating the above steps (1) to (3) until the Q value meets the above requirements.
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