CN113937340B - Battery cell, battery and charging method - Google Patents
Battery cell, battery and charging method Download PDFInfo
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- CN113937340B CN113937340B CN202111553177.0A CN202111553177A CN113937340B CN 113937340 B CN113937340 B CN 113937340B CN 202111553177 A CN202111553177 A CN 202111553177A CN 113937340 B CN113937340 B CN 113937340B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses an electric core, a battery and a charging method.A first reference electrode is arranged at the inner position, and a second reference electrode is arranged at the outer position, so that the ion concentration of the second reference electrode is equivalent to the ion concentration of the central position between a positive electrode and a negative electrode, and the ion concentration of the middle position can be kept unchanged in the charging process, thereby eliminating the influence of the ion concentration on the determination of a lithium-separating potential; meanwhile, the first reference electrode is arranged at a position deviating from the center between the positive electrode and the negative electrode due to the different thicknesses of the first diaphragm and the second diaphragm, so that the limitation on the arrangement position of the first reference electrode can be eliminated, and the battery core has a wide application range. In addition, the charging method in the embodiment of the invention can avoid lithium precipitation of the battery in the charging process, thereby avoiding potential safety hazard, improving the safety of the battery and even the charging process, and providing effective data reference for making a quick charging strategy.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a battery core, a battery and a charging method.
Background
For a lithium ion battery, negative pole lithium separation is an important factor for restricting the charging safety of the lithium ion battery, and the negative pole lithium separation usually occurs on the surface of the negative pole, so how to determine the lithium separation potential on the surface of the negative pole, avoid the lithium separation of the lithium ion battery, and improve the safety of the lithium ion battery is particularly important.
Disclosure of Invention
The embodiment of the invention provides a battery cell, a battery and a charging method, and the lithium-precipitation potential on the surface of a negative electrode can be accurately determined by setting a reference electrode, so that the safety of a lithium ion battery is improved.
In a first aspect, an embodiment of the present invention provides an electrical core, including: a positive electrode, a negative electrode, and a first separator between the positive electrode and the negative electrode;
the battery cell further comprises:
a first reference electrode positioned between the negative electrode and the first separator;
a second separator between the negative electrode and the first reference electrode;
a second reference electrode located on a side of the negative electrode facing away from the first reference electrode;
and a third separator between the second reference electrode and the negative electrode;
wherein a thickness of the first diaphragm is different from a thickness of the second diaphragm.
In a second aspect, an embodiment of the present invention provides a battery, including: the battery cell provided by the embodiment of the invention.
In a third aspect, an embodiment of the present invention provides a charging method, including:
performing charging treatment on the battery provided by the embodiment of the invention, and collecting a first potential of a first reference electrode, a second potential of a second reference electrode and a third potential of a negative electrode in the battery;
determining a lithium-evolution potential of the surface of the negative electrode according to the first potential, the second potential, the third potential, and the thickness of a first separator and the thickness of a second separator in the battery;
adjusting a charging current based on the lithium evolution potential.
The invention has the following beneficial effects:
according to the battery cell, the battery and the charging method provided by the embodiment of the invention, the first reference electrode is arranged between the negative electrode and the positive electrode, and the second reference electrode is arranged on the side of the negative electrode away from the first reference electrode, so that the first reference electrode is arranged at the inner position, and the second reference electrode is arranged at the outer position, so that the ion concentration of the position where the second reference electrode is arranged is equivalent to the ion concentration of the middle position (namely the central position between the positive electrode and the negative electrode), and the ion concentration of the middle position can be kept unchanged in the charging process, and further the ion concentration of the arranged position of the second reference electrode can be kept unchanged in the charging and discharging process, so that the influence of the ion concentration on the determination of the lithium separation potential can be eliminated; meanwhile, the first diaphragm and the second diaphragm are different in thickness, so that the first reference electrode is arranged at a position deviating from the center between the positive electrode and the negative electrode, the limitation on the arrangement position of the first reference electrode can be eliminated on the basis of accurately determining the lithium precipitation potential, and the battery core has a wide application range.
Moreover, based on the battery with the battery cell provided by the embodiment of the invention, when the lithium analysis potential is determined, the lithium analysis potential can be accurately and effectively determined, so that the error is reduced; furthermore, when charging is carried out based on the determined lithium analysis potential, the charging current can be reasonably and effectively adjusted, when the battery is a lithium ion battery, the lithium analysis of the battery in the charging process is avoided, the potential safety hazard is further avoided, the safety of the battery and even the charging process is improved, and effective data reference is provided for the formulation of a quick charging strategy.
Drawings
Fig. 1 is a schematic structural diagram of a battery cell provided in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of another electrical core provided in an embodiment of the present invention;
FIG. 3 is a schematic diagram of a distribution of lithium ion concentration provided in an embodiment of the present invention;
fig. 4 is a schematic structural diagram of another battery cell provided in the embodiment of the present invention;
fig. 5 is a schematic structural diagram of another electrical core provided in an embodiment of the present invention;
fig. 6 is a schematic structural diagram of a battery provided in an embodiment of the present invention;
fig. 7 is a flowchart of a charging method according to an embodiment of the present invention;
FIG. 8 is a graph of test results provided in an embodiment of the present invention;
fig. 9 is a schematic diagram of lithium deposition on the surface of the negative electrode at different potential differences according to the embodiment of the present invention.
10-negative electrode, 11 a-first reference negative electrode, 11 b-second reference negative electrode, 20-positive electrode, 31-first diaphragm, 32-second diaphragm, 33-third diaphragm, 34-fourth diaphragm, 41-first reference electrode, 42-second reference electrode, 43-third reference electrode, 50-insulating film, 100-cell, 200-case.
Detailed Description
Specific embodiments of a battery cell, a battery and a charging method according to embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The inventors have found in their studies that, in the case of a lithium ion battery, the conductivity of the negative electrode is relatively good, and it is considered that the solid phase potentials of the surface at any position of the negative electrode are the same; however, the liquid-phase potential at each position between the positive electrode and the negative electrode is influenced by the lithium ion concentration at the position, and the lithium ion concentration distribution is influenced by the charging and discharging current, the position and the temperature, so that it is difficult to directly perform a test when determining the potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode, that is, the lithium-deposition potential.
Based on this, the embodiment of the invention provides the battery cell, and the first reference electrode and the second reference electrode are arranged, so that the influence of the lithium ion concentration can be avoided, and the lithium-precipitation potential can be accurately and effectively determined.
Specifically, an embodiment of the present invention provides an electrical core, as shown in fig. 1 and fig. 2, including: a positive electrode 20, a negative electrode 10, and a first separator 31 between the positive electrode 20 and the negative electrode 10;
the electric core further comprises:
a first reference electrode 41, the first reference electrode 41 being located between the negative electrode 10 and the first separator 31;
a second separator 32, the second separator 32 being located between the negative electrode 10 and the first reference electrode 41;
a second reference electrode 42, the second reference electrode 42 being located on a side of the negative electrode 10 facing away from the first reference electrode 41;
and a third separator 33, the third separator 33 being located between the second reference electrode 42 and the negative electrode 10;
wherein the thickness of the first diaphragm 31 (d 1 as shown in figure 1) is different from the thickness of the second diaphragm 32 (d 2 as shown in figure 1).
Specifically, in embodiments of the present invention, the first and second reference electrodes may be used to: and determining the lithium precipitation potential of the surface of the negative electrode.
In this way, by arranging the first reference electrode between the negative electrode and the positive electrode and arranging the second reference electrode on the side of the negative electrode away from the first reference electrode, the first reference electrode is arranged at the inner position, and the second reference electrode is arranged at the outer position, so that the ion concentration of the position where the second reference electrode is arranged is equivalent to the ion concentration of the middle position (namely, the central position between the positive electrode and the negative electrode, and the middle positions mentioned in the following content all represent the meaning), and the ion concentration of the middle position can be kept unchanged in the charging process, and further the ion concentration of the arranged position of the second reference electrode can be kept unchanged in the charging and discharging process, thereby eliminating the influence of the ion concentration on the determination of the lithium-out potential; meanwhile, the first diaphragm and the second diaphragm are different in thickness, so that the first reference electrode is arranged at a position deviating from the center between the positive electrode and the negative electrode, the limitation on the arrangement position of the first reference electrode can be eliminated on the basis of accurately determining the lithium precipitation potential, and the battery core has a wide application range.
It should be noted that, taking a battery cell in a lithium ion battery as an example, in an actual application process, the lithium ion concentration between the surface of the positive electrode and the surface of the negative electrode is in a linear distribution when charging and discharging are stable;
for example, as shown in fig. 3, the x-axis represents the distance from the surface of the negative electrode 10, the y-axis represents the lithium ion concentration during charging, the broken line 1 represents the center position between the positive electrode 20 and the negative electrode 10, the solid line s1 represents the lithium ion concentration distribution curve between the positive electrode 20 and the negative electrode 10 at static equilibrium, the solid line s2 represents the lithium ion concentration distribution curve between the positive electrode 20 and the negative electrode 10 at a charging magnification of 1, and the solid line s3 represents the lithium ion concentration distribution curve between the positive electrode 20 and the negative electrode 10 at a charging magnification of 2; as can be seen from fig. 3, the lithium ion concentration remains constant at the position of the dashed line 1 during charging.
Therefore, through setting up the second reference electrode for the lithium ion concentration of second reference electrode position can reach the effect when setting up the position of dotted line 1, and then can solve how to set up the reference electrode in the position that the charging process lithium ion concentration does not change, thereby can effectively, accurately determine and analyse the lithium potential.
It is emphasized that, in the embodiment of the present invention, since the thickness of the first diaphragm is different from that of the second diaphragm, the arrangement position of the first reference electrode is necessarily not located at the middle position (i.e., the position where the dotted line 1 in fig. 1 is located), i.e., the first reference electrode is offset from the middle position; the second reference electrode is combined, even if the first reference electrode deviates from the middle position, the accuracy of the determined lithium analysis potential can be still ensured, and the influence of the ion concentration on the lithium analysis potential is eliminated, so that the setting position of the first reference electrode is more flexible without being limited by the middle position, the flexible setting can be carried out according to actual needs, the needs of different application scenes are met, and meanwhile, the application field and the application range of the battery cell can be improved.
In actual conditions, the outside of electric core can be provided with insulating material, and when electric core was used to the battery, electric core generally set up the inside at the casing of battery, if the casing adopts the metal material preparation, through the insulating material of electric core outside, can avoid taking place the short circuit between electric core and the casing, and then can guarantee the charge-discharge that the battery can be normal.
Therefore, optionally, in the embodiment of the present invention, the first separator is further disposed at the outermost side of the battery cell in the first direction; wherein the first direction is: the arrangement direction of the positive electrode and the negative electrode;
the first diaphragm that is located the outermost side is multiplexing to be the third diaphragm, and electric core still includes: the insulating film is arranged on the side, away from the negative electrode, of the second reference electrode; alternatively, the second reference electrode is disposed between the outermost first separator and the third separator.
For example, as shown in fig. 1, the direction F1 is a first direction, the first separator 31 located on the left side of the negative electrode 10 in the figure is the outermost first separator (also denoted by 31), and the first separator 31 can be reused as the third separator 33, and in this case, only the second reference electrode 42 needs to be disposed on the surface (i.e., the left surface) of the first separator 31 facing away from the negative electrode 10; meanwhile, in order to avoid short circuit when the cell is applied to a battery, an insulating film 50 may be provided on a side surface (i.e., a left side surface) of the second reference electrode 42 facing away from the negative electrode 10.
For another example, as shown in fig. 2, the first separator located on the left side of the negative electrode 10 in the drawing is the outermost first separator 31, and the outermost first separator 31 is not reused as the third separator 33, but the third separator 33 is provided alone such that the outermost first separator 31, the second reference electrode 42, the third separator 33, and the negative electrode 10 are arranged in this order along the direction F1; since the first separator 31 located at the outermost side is located at the outermost side, it is not necessary to provide an insulating film at this time.
Therefore, in specific implementation, the second reference electrode and the third diaphragm can be arranged according to actual needs, so that the flexibility of design is improved, and the requirements of different application scenarios are met.
Optionally, in the embodiment of the present invention, the positive electrode, the negative electrode, and the first separator are provided in plurality, and the positive electrode and the negative electrode are alternately provided;
at least one negative electrode is disposed between the first reference electrode and the second reference electrode.
To illustrate, when the positive electrode and the negative electrode are alternately disposed, insulation between the negative electrode and the positive electrode needs to be achieved through the first separator to avoid short circuit between the positive electrode and the negative electrode.
For example, as shown in fig. 4, the cathode located at the outermost side has two cathodes, which may be defined as a first reference cathode (indicated by 11 a) and a second reference cathode (indicated by 11 b), respectively, the first reference electrode 41 is located at a side (i.e., right side) of the first reference cathode 11a close to the cathode 20, and the second reference electrode 42 is located at a side (i.e., left side) of the first reference cathode 11a away from the cathode 20; that is, one negative electrode (i.e., the first reference negative electrode 11 a) is provided between the first reference electrode 41 and the second reference electrode 42.
In fig. 4, the first reference electrode 41 and the second reference electrode 42 are disposed only on the left and right sides of the first reference negative electrode 11a, and the first reference electrode 41 and the second reference electrode 42 are not disposed around the second reference negative electrode 11 b.
Of course, alternatively, it can also be set as:
the first reference electrode 41 and the second reference electrode 42 are provided only on the left and right sides of the second reference anode 11b, and illustration is not given;
alternatively, the first reference electrode 41 and the second reference electrode 42 are provided not only on the left and right sides of the first reference anode 11a, but also the first reference electrode 41 and the second reference electrode 42 are provided on the left and right sides of the second reference anode 11b, not shown;
therefore, when the first reference electrode and the second reference electrode are arranged, the arrangement can be carried out according to actual needs, so that the flexibility of design is improved, and the requirements of different application scenes are met.
In addition, the first reference electrode and the second reference electrode are arranged around the first reference negative electrode, namely around the negative electrode on the outermost side, so that the arrangement difficulty of the first reference electrode and the second reference electrode can be reduced, the first reference electrode and the second reference electrode can be conveniently introduced into the battery cell, the manufacturing effect of the battery cell is improved, and the manufacturing process is simplified.
The above example describes a case where one negative electrode is disposed between the first reference electrode and the second reference electrode, and of course, two, three, or four negative electrodes may also be disposed between the first reference electrode and the second reference electrode, and the negative electrodes may be specifically disposed according to actual needs, so as to improve flexibility of design and meet needs of different application scenarios.
Alternatively, in an embodiment of the present invention, as shown in fig. 1, the thickness of the first septum 31 (denoted by d 1) is greater than the thickness of the second septum 32 (denoted by d 2);
the thickness d1 of the first diaphragm 31 is equal to the thickness of the third diaphragm 33 (denoted by d 3).
If the cell is referred to as an initial cell before the first and second reference electrodes are inserted, the initial cell includes: the battery comprises a positive electrode, a negative electrode and a first diaphragm, wherein the first diaphragm is needed to be arranged between the positive electrode and the negative electrode and is also arranged on the outermost side of an initial battery core;
when the second reference electrode is arranged, if the second reference electrode is arranged on the surface of the outermost first separator (as shown in fig. 1) away from the negative electrode, then there is no need to additionally arrange a third separator, that is, the outermost first separator is reused as the third separator;
therefore, the manufacturing steps of the third diaphragm can be reduced, the manufacturing process of the battery cell is simplified, and the manufacturing efficiency of the battery cell is improved.
In addition, the thickness of the first diaphragm is smaller than that of the second diaphragm, so that the thickness of the first diaphragm is smaller, the problem of local thickness increase caused by adding the first reference electrode can be further avoided, and the local thickness increase of the battery core is avoided.
Of course, alternatively, for the thickness d3 of the third diaphragm, it may also be provided that:
d1＞d2＞d3；
or, d3 > d1 > d 2;
or, d1 > d3 > d 2.
That is, the thickness d3 of the third diaphragm can be set according to actual requirements, so as to improve the flexibility of design and meet the requirements of different application scenarios.
Alternatively, in the present embodiment, the thickness d1 of the first diaphragm may be set to be, but not limited to, 16 μm, and the thickness d2 of the second diaphragm may be set to be, but not limited to, 5.5 μm.
Of course, the thicknesses of the first diaphragm and the second diaphragm are not limited to the specific values, and may be set to other values according to actual needs, and are not limited herein.
Optionally, in an embodiment of the present invention, as shown in fig. 5, the battery cell further includes:
a third reference electrode 43, the third reference electrode 43 being located between the first separator 31 closest to the first reference electrode 41 and the positive electrode 20;
and a fourth diaphragm 34, the fourth diaphragm 34 being located between the third reference electrode 43 and the positive electrode 20 closest to the first reference electrode 41.
Wherein the third reference electrode can be used to: and (3) determining the lithium-precipitation potential of the surface of the negative electrode by matching the first reference electrode and the second reference electrode.
Referring to fig. 5, the center position between the positive electrode and the negative electrode is shown as a position shown by a dashed line 2, and therefore, in the embodiment of the present invention, both the first reference electrode 41 and the third reference electrode 43 are disposed at positions deviated from the middle position, that is, both the first reference electrode 41 and the third reference electrode 43 are disposed at positions where the ion concentration changes during the charging process (in this case, both the first reference electrode 41 and the third reference electrode 43 may be referred to as dynamic reference electrodes), but, by the second reference electrode 42 (which may be referred to as static reference electrode because the ion concentration at the positions remains unchanged during the charging process), it is still ensured that the determined lithium deposition potential is not affected by the ion concentration, so that the accuracy of the result of determining the lithium deposition potential is ensured, and the restriction on the disposed positions of the first reference electrode and the third reference electrode is reduced, the application range is expanded.
Specifically, in the embodiment of the present invention, the thickness of the second diaphragm (as shown by d2 in fig. 5) may be equal to the thickness of the fourth diaphragm (as shown by d4 in fig. 5), and both of the thicknesses are smaller than the thickness of the first diaphragm, so that the thickness of the fourth diaphragm may also be set to be thinner, and further, the problem of local thickness increase caused when the third reference electrode is added can be avoided, thereby avoiding local thickness increase of the battery cell;
of course, the thickness of the second diaphragm may not be equal to the thickness of the fourth diaphragm, and the specific setting of the thickness of the fourth diaphragm may be set according to actual needs, which is not limited herein, so as to improve the flexibility of design and meet the needs of different application scenarios.
Specifically, in the embodiment of the present invention, the number of the reference electrodes disposed between the positive electrode and the negative electrode is not limited to two (i.e., the first reference electrode and the third reference electrode), and may also be three, four, or five, and other numbers, and may be set according to actual needs, so as to improve flexibility of design and meet needs of different application scenarios.
Optionally, in an embodiment of the present invention, the first diaphragm, the second diaphragm, the third diaphragm, and the fourth diaphragm are made of the same material.
So, can avoid the inconsistent ion transmission ability's that leads to of preparation material difference, and then avoid the influence to the charge-discharge capacity of electric core to improve the reliability of electric core.
Of course, optionally, the manufacturing materials of the first diaphragm, the second diaphragm, the third diaphragm and the fourth diaphragm may also be set to be at least partially different, and the normal charge and discharge functions of the battery cell can be ensured by the setting of the first diaphragm, the second diaphragm, the third diaphragm and the fourth diaphragm, which all belong to the protection scope of the embodiment of the present invention.
Specifically, the selection of the materials for manufacturing the first diaphragm, the second diaphragm, the third diaphragm and the fourth diaphragm may be set according to actual needs, as long as the materials can perform an insulating function and simultaneously realize the transmission of ions, and the selection is not limited herein.
Optionally, in the embodiment of the present invention, the first reference electrode and the third reference electrode are made of the same material;
the first reference electrode and the second reference electrode are made of different materials.
Therefore, adverse effects on the charge and discharge performance of the battery cell due to inconsistent manufacturing materials of the first reference electrode and the third reference electrode can be avoided, so that the battery cell has higher reliability; meanwhile, the first reference electrode and the second reference electrode are made of different materials, so that the flexibility of reference electrode manufacturing can be improved, and the requirements of different application scenes can be met.
Specifically, in the embodiment of the present invention, the first reference electrode and the third reference electrode are made of materials including copper wires;
the cell is applied to a lithium ion battery, and the second reference electrode is made of a lithium sheet.
Certainly, the first reference electrode and the third reference electrode are not limited to copper wires and can be made of other conductive materials, and meanwhile, the second reference electrode is not limited to lithium sheets and can be made of other conductive materials; the specific setting can be carried out according to actual needs, and is not limited herein.
It should be noted that, in practical applications, it is difficult to place the reference electrode completely in the middle between the positive electrode and the negative electrode; therefore, according to the fact that the ion concentration between the surface of the positive electrode and the surface of the negative electrode is in linear distribution during charging and discharging, the ion concentration at the middle position is basically not changed, so that the ion concentration at the position where the second reference electrode is located and the reference electrode placed at the middle position can achieve similar effects, and further it can be considered that:
the potential difference between the negative electrode and the second reference electrode under test is the potential difference between the negative electrode relative to the reference electrode between the positive and negative electrodes.
Therefore, by providing a second reference electrode at a position where the ion concentration does not change during charge and discharge, and at least one reference electrode (e.g., a first reference electrode and a third reference electrode) which is in a dynamic state, a potential linear equation at positions having different distances from the surface of the negative electrode can be obtained from the potential of the first reference electrode, the potential of the second reference electrode, the potential of the third reference electrode, and the distance between the reference electrodes, and thus a negative reference potential difference (i.e., a potential difference between the potential of the first reference electrode and the solid phase potential of the surface of the negative electrode, and a potential difference between the potential of the third reference electrode and the solid phase potential of the surface of the negative electrode) at any position between the surfaces of the positive and negative electrodes can be obtained.
Based on the same inventive concept, an embodiment of the present invention provides a battery, as shown in fig. 6, including: the battery cell 100 provided in the embodiment of the present invention is described above.
To illustrate, only a portion of the battery cells 100 is shown in fig. 6.
Optionally, in an embodiment of the present invention, as shown in fig. 6, the battery may further include: and the battery cell 100 is positioned inside the casing 200.
Optionally, in the embodiment of the present invention, the battery may further include other structures besides the battery core and the casing, such as, but not limited to, a cover plate, and the like.
Wherein, for the cover plate, the cover plate may include: other structures such as a pole column and an explosion-proof valve;
the pole column can be electrically connected with a pole lug in the battery cell and is used for leading out the anode and the cathode;
the explosion-proof valve is used for: when the internal temperature of the battery is higher, heat is released, and the thermal runaway of the battery is avoided.
Certainly, the battery cell provided in the embodiment of the present invention is provided with reference electrodes (including the first reference electrode, the second reference electrode, and the third reference electrode), so that the cover plate may be provided with terminals corresponding to the reference electrodes, in addition to the terminals corresponding to the positive electrode and the negative electrode, or may be provided with terminals corresponding to the reference electrodes, but the reference electrodes are led out through other structures, so as to facilitate subsequent tests.
Optionally, in the embodiment of the present invention, the battery may be, but not limited to, a lithium ion battery, and may also be other types of batteries, and may be specifically set according to actual needs, so long as the battery including the battery cell provided in the embodiment of the present invention belongs to the protection scope of the embodiment of the present invention.
Based on the same inventive concept, an embodiment of the present invention provides a charging method, as shown in fig. 7, including:
s701, performing charging processing on the battery provided in the embodiment of the present invention, and collecting a first potential of a first reference electrode, a second potential of a second reference electrode, and a third potential of a negative electrode in the battery;
when the first potential, the second potential and the third potential are collected, a collection period can be set, and when the collection period is reached, all potentials are collected;
specifically, the acquisition period can be set to be shorter, so that the acquisition interval is favorably reduced, real-time acquisition is realized, and the real-time monitoring on the subsequent lithium analysis potential is realized; of course, the acquisition period can also be set to be larger so as to reduce the operation processing amount and reduce the power consumption;
therefore, the setting of the acquisition period may be performed according to actual needs, and is not limited herein.
S702, determining the lithium precipitation potential of the surface of the negative electrode according to the first potential, the second potential, the third potential, the thickness of the first diaphragm and the thickness of the second diaphragm in the battery;
and S703, adjusting the charging current based on the lithium precipitation potential.
So, through the first electric potential, the second electric potential and the third electric potential of gathering, can determine the lithium potential of analysing on negative pole surface, the lithium potential of analysing that can also guarantee simultaneously to determine has higher degree of accuracy.
And through the setting to first reference electrode and second reference electrode in the electric core, can accurately determine and analyse the lithium potential, in applying to lithium ion battery, and when analysing lithium potential and being close to 0 or being less than 0, take measures immediately, avoid the negative pole to take place to analyse lithium to avoid dangerous emergence, improve the security and the reliability of battery.
In addition, through monitoring the lithium analysis potential on the surface of the negative electrode, more accurate data input can be provided for the formulation of a quick charge strategy of the battery, and reference data is provided for control factors of high-rate charge and discharge.
Optionally, in an embodiment of the present invention, when the method is applied to a lithium ion battery, and the first reference electrode is made of a copper wire, before performing S701, the method further includes:
the first reference electrode is subjected to a lithium plating treatment.
Therefore, the first reference electrode can have lithium element, and the subsequent determination of the lithium precipitation potential is facilitated.
Specifically, the specific process of the lithium plating treatment can be referred to in the prior art, and is not limited herein.
Optionally, in an embodiment of the present invention, the lithium deposition potential on the surface of the negative electrode is: when the potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode is larger than the first potential, the second potential, the third potential, the thickness of the first diaphragm and the thickness of the second diaphragm in the battery, the lithium precipitation potential on the surface of the negative electrode is determined, and the method specifically comprises the following steps:
determining a reference potential difference corresponding to the potential change caused by the second membrane according to the first potential, the second potential, the thickness of the first membrane and the thickness of the second membrane;
taking the difference between the first potential and the reference potential difference as the liquid phase potential of the surface of the negative electrode;
and taking the difference value of the third potential and the liquid phase potential as the potential difference between the solid phase potential on the surface of the negative electrode and the liquid phase potential on the surface of the negative electrode.
Therefore, through the potentials and the thicknesses of the diaphragms, the potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode can be determined, and when the potential difference is applied to the lithium ion battery and the potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode is close to 0 or less than 0, measures are taken immediately to avoid lithium precipitation of the negative electrode, so that danger is avoided, and the safety and the reliability of the battery are improved.
And through the process, the liquid phase potential at any position between the anode and the cathode can be determined, and then the potential difference between the potential at any position between the anode and the cathode and the solid phase potential on the surface of the cathode can be determined, so that the liquid phase potential on the surface of the cathode can be monitored.
Alternatively, in the embodiment of the present invention, the following formula (formula 1) may be adopted to calculate the potential difference between the solid-phase potential of the anode surface and the liquid-phase potential of the anode surface:
φs-φe=V1-[2d2/(d1-d2)]×(V2-V1)；
V1=φs-φe1；
V2=φs-φe2；
wherein phi ise1Represents a first potential, phie2Represents a second potential, d1Denotes the thickness of the first diaphragm, d2Denotes the thickness of the second diaphragm, phisRepresents the solid phase potential of the surface of the negative electrode, [ phi ]eIndicating the liquid phase potential at the surface of the negative electrode.
Specifically, the liquid-phase potential φ of the anode surfaceeThe following formula (denoted as formula 2) can be used:
φe=φe1-[2d2/(d1-d2)]×(φe2-φe1)；
by transforming equation 2, equation 1 can be obtained.
To illustrate, in the above equation 2, the left side of the equation represents the liquid phase potential of the cathode surface, and the right side of the equation [2d ]2/(d1-d2)]×(φe2-φe1) A reference potential difference representing a potential change induced by the second membrane and related to:
the distance between the first reference electrode and the second reference electrode (denoted as distance 1);
the potential difference between the first potential and the second potential (i.e., + -)e2-φe1）；
Here, since the ion concentration of the position where the second reference electrode is disposed corresponds to the ion concentration of the intermediate position, the distance 1 may be: (d)1+d2)/2-d2=(d1-d2) 2; the reference potential difference is then: (phi)e2-φe1)/[(d1-d2)/2]×d2Then after transformation, the [2d ] can be obtained2/(d1-d2)]×(φe2-φe1)。
Thus, regardless of d1And d2The potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode can be obtained at any value, and thus the potential difference between any position between the positive electrode and the negative electrode and the solid-phase potential on the surface of the negative electrode can be determined.
Optionally, in this embodiment of the present invention, if the battery cell further includes a third reference electrode, and the thickness of the fourth separator is equal to the thickness of the second separator, determining a potential difference between a solid-phase potential on the surface of the negative electrode and a liquid-phase potential on the surface of the negative electrode, specifically including:
the potential difference is calculated using the following formula:
φ1=V1-(d2/d1 )×(V3-V1) (ii) a (formula 3)
V1=φs-φe1；
V3=φs-φe3；
φ2=V1-(2d2/d1)×(V2-V1) (ii) a (formula 4)
V1=φs-φe1；
V2=φs-φe2；
φs-φe=(φ1+φ2) 2; (formula 5)
Wherein phi ise3Represents a third potential, phi, of the third reference electrode1Represents the potential difference (noted as potential difference 1) between the solid-phase potential of the surface of the negative electrode and the liquid-phase potential of the surface of the negative electrode calculated based on the first reference electrode and the third reference electrode2Represents the potential difference (noted as potential difference 2) between the solid-phase potential at the surface of the negative electrode and the liquid-phase potential at the surface of the negative electrode, calculated based on the first reference electrode and the second reference electrode.
The calculation of the potential difference 1 and the potential difference 2 can be referred to the above explanation of equation 1, and will not be described in detail here.
To explain this point, since the thickness of the fourth diaphragm is equal to that of the second diaphragm, the thickness of the fourth diaphragm is also expressed by d2 in equation 3 and equation 4.
Therefore, the potential difference 1 and the potential difference 2 are respectively calculated, and the final potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode is obtained based on the average value of the potential difference 1 and the potential difference 2, so that the influence of errors caused by the arrangement of a certain reference electrode can be eliminated, and the accuracy of a determination result is improved.
It should be noted that, if the number of the reference electrodes is not limited to the first reference electrode, the second reference electrode, and the third reference electrode, that is, the number of the dynamic reference electrodes is not limited to two (that is, the first reference electrode and the third reference electrode), if more (for example, three or four) reference electrodes are provided, the potential difference may be calculated based on the first reference electrode, based on each of the other reference electrodes (that is, the reference electrodes other than the first reference electrode) and the first reference electrode, and then the average value of the potential differences is calculated, and the average value is used as the potential difference between the solid-phase potential on the final negative electrode surface and the liquid-phase potential on the negative electrode surface, so that the accuracy of the determination result may be effectively improved.
Optionally, in an embodiment of the present invention, adjusting the charging current based on the lithium deposition potential specifically includes:
when the current voltage of the battery is greater than the preset voltage, judging whether the currently determined lithium analysis potential is equal to zero or not;
if so, reducing the current charging current;
if not, when the duration time of charging by adopting the current charging current reaches the preset time, reducing the current charging current.
Thus, the determined lithium-analyzing potential (namely, the potential difference between the solid-phase potential on the surface of the negative electrode and the liquid-phase potential on the surface of the negative electrode) and the preset time can be used as judgment conditions, and the current charging current can be reduced when the potential difference is equal to zero, so that the potential difference is prevented from being smaller than 0 when the charging is continued with the current charging current, and further the occurrence of lithium analysis is avoided; and when the potential difference is not equal to zero (or can be understood as the potential difference is greater than zero), the current charging current is still reduced no matter whether the potential difference is equal to zero or not by judging the preset time when the preset time is reached, so that the potential difference possibly caused when the charging is continued with the current charging current is less than 0, the risk is effectively avoided, and the safety of the charging process is improved.
The following description will be made with reference to specific examples.
Example (b): based on the above battery provided in the embodiment of the present invention, when the battery is charged and the charging strategy is adopted for charging, the variation of the charging current and the variation of the potential difference are shown in fig. 8, the specific charging process corresponding to the battery is shown in table 1 below, a solid line 1 in fig. 8 represents the variation of the charging rate in the charging process, and only shows a part of the charging rate in the charging process corresponding to the solid line 1.
TABLE 1
The charging rates in table 1 correspond to different charging currents, and the charging current at any one charging rate is constant, i.e., a constant current charging process.
In conjunction with the illustration of fig. 8 and the illustration of table 1, the following conclusions can be determined:
1. in the process from the serial number 1 to the serial number 5, the potential difference is always larger than 0, so that lithium precipitation does not occur in the negative electrode, the charging rate is gradually increased, and the charging current is gradually increased.
2. The conversion condition from the process step with the sequence number 1 to the process step with the sequence number 2 is as follows: whether the standing time meets the preset duration or not;
for example, in the process step No. 1, when the standing time reaches 20min, the conversion condition is satisfied, the charging rate is adjusted to 1C, that is, the constant current charging for the battery is started, and the process step from the process step No. 1 is converted to the process step No. 2.
3. The conversion conditions from the process step with sequence number 2 to the process step with sequence number 4 are: whether the charging voltage meets a preset value or not;
for example, taking the process step No. 2 as an example, in the process step No. 2, if the charging voltage reaches 3.55V, that is, if the conversion condition is satisfied, the charging rate can be increased from 1C to 1.5C, and the process step from the process step No. 2 to the process step No. 3 is realized.
4. Starting from the process step with the sequence number 5, the conversion conditions are as follows: a potential difference and a duration of charging;
for example, taking the process step numbered 5 as an example, if the potential difference is always greater than 0 when charging is performed at a discharge rate of 2.5C, and the duration time reaches 15s, the discharge rate is reduced from 2.5C to 2.0C, so that the process step numbered 5 is converted into the process step numbered 6, and the current charging current is reduced.
5. In fig. 8, the curve corresponding to the dashed line s4 represents the variation of the potential difference obtained based on the above battery and charging method provided by the embodiment of the present invention, and it can be found that:
when the charging process (namely, the step charging process) corresponding to the solid line 1 is adopted, the potential difference is always greater than or equal to 0, so that the lithium precipitation of the negative electrode can be avoided in the whole charging process, and the safety and the reliability of the charging process can be ensured.
6. For comparison, a reference test is given, and the curve corresponding to the dashed line s5 shows the variation of the potential difference obtained on the basis of the three-electrode cell of the prior art (i.e. the cell incorporating the reference electrode) and the charging process using the solid line 1, it can be found that:
when the same charging procedure is used, in particular at the moment of the reduction of the discharge rate from 2.5C to 2.0C, the ordinate of the broken line s5 corresponds to-0.06795V, clearly less than 0, while the ordinate of the broken line s4 corresponds to 0.00795V, clearly greater than 0;
and the two batteries at the moment when the discharge multiplying power is reduced from 2.5C to 2.0C are structurally disassembled, and no lithium precipitation occurs in the two batteries;
that is to say, the battery provided by the embodiment of the invention can accurately determine the potential difference, and further can effectively guide the formulation of the charging strategy.
Example (b): based on the battery provided by the embodiment of the invention, the battery with the potential difference of 0mV, -21mV and-32 mV is selected and structurally disassembled, and the result is shown in FIG. 9;
wherein, the graph (a) shows a photograph of the surface of the negative electrode at a potential difference of 0mV, which makes it possible to confirm that no lithium deposition occurs on the surface of the negative electrode;
graph (b) shows a photograph of the surface of the negative electrode at a potential difference of-21 mV, which confirmed that lithium deposition had occurred on the surface of the negative electrode, except that less lithium was deposited, as shown in the dashed line box in graph (b);
graph (c) shows a photograph of the surface of the negative electrode at a potential difference of-32 mV, and it can be confirmed that lithium deposition has occurred on the surface of the negative electrode, and the amount of deposited lithium is larger than that in graph (b), as shown in the dotted line box in graph (c).
Thus, the above two embodiments illustrate:
based on the battery and the charging method provided by the embodiment of the invention, the lithium analysis potential can be accurately determined, the lithium analysis of the battery in the charging process is avoided, the potential safety hazard is further avoided, the safety of the battery and even the charging process is improved, and effective data reference is provided for the formulation of a quick charging strategy.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A battery cell, comprising: a positive electrode, a negative electrode, and a first separator between the positive electrode and the negative electrode;
the battery cell further comprises:
a first reference electrode positioned between the negative electrode and the first separator;
a second separator between the negative electrode and the first reference electrode;
a plurality of second reference electrodes are arranged on the negative electrode, and the second reference electrode is positioned on the side, away from the first reference electrode, of the negative electrode on the outermost side;
and a third separator between the second reference electrode and the negative electrode;
wherein a thickness of the first diaphragm is different from a thickness of the second diaphragm.
2. The battery cell of claim 1, wherein the positive electrode, the negative electrode, and the first separator are each provided in plurality, and the positive electrode and the negative electrode are alternately provided;
at least one of the negative electrodes is disposed between the first reference electrode and the second reference electrode.
3. The electrical core of claim 1, wherein a thickness of the first separator is greater than a thickness of the second separator;
the thickness of the first diaphragm is equal to the thickness of the third diaphragm.
4. The cell of claim 1, wherein the first separator is further disposed in the cell outermost in the first direction; wherein the first direction is: the arrangement direction of the positive electrode and the negative electrode;
the first separator located at the outermost side is reused as the third separator, and the battery cell further includes: an insulating film provided on a side of the second reference electrode facing away from the negative electrode;
alternatively, the second reference electrode is disposed between the first separator and the third separator located at the outermost side.
5. The cell of any one of claims 1-4, further comprising:
a third reference electrode positioned between the first separator closest to the first reference electrode and the positive electrode;
and a fourth membrane positioned between the third reference electrode and the positive electrode closest to the first reference electrode.
6. The cell of claim 5, wherein the first reference electrode and the third reference electrode are made of materials comprising copper wire;
the battery core is applied to a lithium ion battery, and the second reference electrode is made of a lithium sheet.
7. A battery, comprising: the cell of any of claims 1-6.
8. A method of charging, comprising:
performing a charging process on the battery of claim 7, and collecting a first potential of a first reference electrode, a second potential of a second reference electrode, and a third potential of a negative electrode in the battery; wherein the ion concentration of the position of the second reference electrode is kept unchanged in the charging process;
determining a lithium-evolution potential of the surface of the negative electrode according to the first potential, the second potential, the third potential, and the thickness of a first separator and the thickness of a second separator in the battery; wherein the lithium-precipitating potential of the surface of the negative electrode is as follows: a potential difference between a solid-phase potential of the negative electrode surface and a liquid-phase potential of the negative electrode surface;
adjusting a charging current based on the lithium evolution potential.
9. The charging method according to claim 8, wherein determining the lithium-evolving potential of the surface of the negative electrode based on the first potential, the second potential, the third potential, and the thickness of the first separator and the thickness of the second separator in the battery specifically comprises:
determining a reference potential difference corresponding to the potential change caused by the second membrane according to the first potential, the second potential, the thickness of the first membrane and the thickness of the second membrane;
taking the difference between the first potential and the reference potential difference as the liquid phase potential of the surface of the negative electrode;
and taking the difference value of the third potential and the liquid phase potential as the potential difference between the solid phase potential of the surface of the negative electrode and the liquid phase potential of the surface of the negative electrode.
10. The charging method according to claim 8, wherein adjusting the charging current based on the lithium deposition potential comprises:
when the current voltage of the battery is greater than a preset voltage, judging whether the currently determined lithium analysis potential is equal to zero or not;
if so, reducing the current charging current;
if not, when the duration time of charging by adopting the current charging current reaches the preset time, reducing the current charging current.
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| CN203910934U (en) * | 2014-04-16 | 2014-10-29 | 河南新太行电源有限公司 | Lithium ion battery monitoring structure |
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| CN203910934U (en) * | 2014-04-16 | 2014-10-29 | 河南新太行电源有限公司 | Lithium ion battery monitoring structure |
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