CN115832285B - Positive electrode material, preparation method thereof, positive electrode plate, secondary battery, battery module, battery pack and power utilization device - Google Patents
Positive electrode material, preparation method thereof, positive electrode plate, secondary battery, battery module, battery pack and power utilization device Download PDFInfo
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- CN115832285B CN115832285B CN202210045439.0A CN202210045439A CN115832285B CN 115832285 B CN115832285 B CN 115832285B CN 202210045439 A CN202210045439 A CN 202210045439A CN 115832285 B CN115832285 B CN 115832285B
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- lithium
- positive electrode
- electrode material
- polyanion
- secondary battery
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910013302 LiMS Inorganic materials 0.000 claims abstract description 7
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
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- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
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- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
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Classifications
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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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
本申请涉及二次电池技术领域，尤其是涉及一种正极材料及制备方法、正极极片、二次电池、电池模组、电池包、用电装置。本申请的正极材料，包括锂的含氧化合物和含有聚阴离子的锂硫化物，所述含有聚阴离子的锂硫化物化学式为LiMS(2‑x)(XOm)x，其中，0＜x＜2，0＜m≤4；M选自Fe、V、Nb、Zr、Mn中的至少一种，X选自P、Si、S、As、Mo、W、B中的至少一种。本申请将聚阴离子与锂硫化物混合，由于聚阴离子的加入，降低了锂硫化物中的硫离子的p轨道能量，使化合物体系的共价性降低，d轨道与p轨道间的杂化减少，化合物中过渡金属的d轨道参与氧化还原反应的份额增加，提高了二次电池材料的放电平台，能够提升其在低SOC下的放电功率。
The present application relates to the technical field of secondary batteries, and in particular to a positive electrode material and preparation method, a positive electrode plate, a secondary battery, a battery module, a battery pack, and an electrical device. The positive electrode material of the present application includes an oxygen-containing compound of lithium and a lithium sulfide containing a polyanion, wherein the chemical formula of the lithium sulfide containing the polyanion is LiMS (2‑x) (XO m ) x , wherein 0＜x＜2, 0＜m≤4; M is selected from at least one of Fe, V, Nb, Zr, and Mn, and X is selected from at least one of P, Si, S, As, Mo, W, and B. The present application mixes the polyanion with the lithium sulfide. Due to the addition of the polyanion, the p orbital energy of the sulfur ion in the lithium sulfide is reduced, the covalency of the compound system is reduced, the hybridization between the d orbital and the p orbital is reduced, and the proportion of the d orbital of the transition metal in the compound participating in the redox reaction is increased, thereby improving the discharge platform of the secondary battery material and being able to improve its discharge power at low SOC.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a positive electrode material, a preparation method, a positive electrode plate, a secondary battery, a battery module, a battery pack and an electric device.
Background
With the rapid development of the new energy field, the secondary battery is widely applied to various large-scale power devices, energy storage systems and various consumer products by virtue of the advantages of excellent charge and discharge chemical properties, no memory effect, small environmental pollution and the like. In recent years, electric devices such as smart phones and electric vehicles have been widely used, and lithium ion secondary batteries have been widely used.
However, with increasing demands of customers, certain electrochemical properties of lithium ion secondary batteries, particularly low discharge power of the secondary batteries at low SOC, have put higher demands on the development of lithium ion secondary batteries.
Disclosure of Invention
The present application has been made in view of the above problems, and an object of the present application is to provide a positive electrode material, a method for producing the same, a positive electrode sheet, a secondary battery, a battery module, a battery pack, and an electric device, which greatly improve the discharge power of the secondary battery in a low State of Charge (SOC) State.
The first aspect of the present application provides a positive electrode material comprising an oxygen-containing compound of lithium and a polyanion-containing lithium sulfide, the polyanion-containing lithium sulfide being a compound represented by formula I:
LiMS (2-x)(XOm)x A I
Wherein 0< X <2,0< m < 4;M > is selected from at least one of iron (Fe), vanadium (V), niobium (Nb), zirconium (Zr) and manganese (Mn), and X is selected from at least one of phosphorus (P), silicon (Si), sulfur (S), arsenic (As), molybdenum (Mo), tungsten (W) and boron (B).
According to the application, the polyanion is mixed with the lithium sulfide, and the p orbit energy of the sulfide ions in the lithium sulfide is reduced due to the addition of the polyanion, so that the covalency of a compound system is reduced, the hybridization between d orbits and p orbits is reduced, the share of the transition metal d orbits in the compound participating in the oxidation-reduction reaction is increased, and meanwhile, the voltage platform of the transition metal is generally higher than that of the sulfide ions, so that the total voltage platform of the system can be improved, the discharge platform of the secondary battery material is improved, and the discharge power of the secondary battery material under low SOC is improved.
In any embodiment, the mass percent of the polyanion-containing lithium sulfide is 3% to 10%, alternatively 3% to 5%, based on the total mass of the positive electrode material.
According to the application, the mass percentage of lithium sulfide containing polyanion is controlled to be 3% -10%, so that a good condition is provided for the complete reaction of ionic polymerization of lithium sulfide, the p-orbit energy of sulfide ions in lithium sulfide is greatly reduced, the covalent nature in a compound system is also greatly reduced, the hybridization between d-orbitals and p-orbitals is reduced, the share of d-orbitals of transition metal in the compound participating in oxidation-reduction reaction is increased, and meanwhile, the voltage platform of the transition metal is generally higher than the voltage platform of sulfide ions, so that the total voltage platform of the system can be improved, the discharge platform of a secondary battery material is improved, and the discharge power of the secondary battery material under low SOC is improved.
In any embodiment, the specific surface area of the positive electrode material is 3.5m 2/g～7m2/g. The application can well control the particle size of the positive electrode material by reasonably controlling the specific surface area of the positive electrode material, so that the discharge power performance of the secondary battery at low SOC is greatly improved.
In any embodiment, the lithium oxygen-containing compound includes lithium transition metal oxide and/or olivine structured lithium-containing phosphate, the lithium transition metal oxide is selected from at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide, and modified compounds thereof, and the olivine structured lithium-containing phosphate is selected from at least one of lithium iron phosphate, a composite of lithium iron phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon, lithium manganese iron phosphate, and a composite of lithium manganese iron phosphate and carbon.
According to the application, the lithium-containing phosphate with a lithium transition metal oxide and/or olivine structure is added, so that the share of transition metal is increased, the share of d orbits of the transition metal in the anode material participating in oxidation-reduction reaction is ensured to be enough, and the voltage platform of the transition metal is generally higher than that of sulfur ions, so that the total voltage platform of the system is greatly improved, and the discharge power performance of the secondary battery under low SOC is improved.
The second aspect of the present application provides a method for preparing a positive electrode material, comprising the steps of:
Providing a mixture of Li 2 S, metal M, sulfur powder and Li 2XOm, performing ball milling, screening and sintering to obtain lithium sulfide containing polyanion, and mixing the lithium sulfide containing polyanion with an oxygen-containing compound of lithium to obtain a positive electrode material;
wherein the positive electrode material is a polyanion-containing lithium sulfide having the formula I:
LiMS (2-x)(XOm)x A I
0< X <2,0< m < 4;M > is selected from at least one of iron (Fe), vanadium (V), niobium (Nb), zirconium (Zr) and manganese (Mn), and X is selected from at least one of phosphorus (P), silicon (Si), sulfur (S), arsenic (As), molybdenum (Mo), tungsten (W) and boron (B).
According to the application, lithium sulfide (Li 2 S), metal M, sulfur powder and Li 2XOm are mixed according to a certain proportion, and then ball milling, screening and sintering are carried out to obtain the lithium sulfide containing polyanion, and then the lithium sulfide containing polyanion and the oxygen-containing compound of lithium are mixed according to a certain proportion to obtain the anode material.
According to the application, the polyanion is mixed with the lithium sulfide, and the p orbit energy of the sulfide ions in the lithium sulfide is reduced due to the addition of the polyanion, so that the covalency of a compound system is reduced, the hybridization between d orbits and p orbits is reduced, the share of the transition metal d orbits in the compound participating in the oxidation-reduction reaction is increased, and meanwhile, the voltage platform of the transition metal is generally higher than that of the sulfide ions, so that the total voltage platform of the system can be improved, the discharge platform of the secondary battery material is improved, and the discharge power of the secondary battery material under low SOC is improved.
In any embodiment, in the ball milling step, the ball milling time is 24-48 h, the ball milling rotating speed is 500-800 r, and the ball-material ratio is 50:1-100:1. According to the application, through reasonably setting the ball milling ratio, the ball milling rotating speed and the ball milling time, lithium sulfide (Li 2 S), metal M, sulfur powder and Li 2XOm are mixed more uniformly, so that polyanion can be combined with lithium sulfide more deeply, and a good bedding is provided for the subsequent action of polyanion.
A third aspect of the present application provides a positive electrode sheet comprising the positive electrode material of the first aspect of the present application or a positive electrode material produced by the method for producing a positive electrode material of the second aspect of the present application.
A fourth aspect of the present application provides a secondary battery comprising the positive electrode tab of the third aspect of the present application.
A fifth aspect of the present application provides a battery module comprising the secondary battery of the fourth aspect of the present application.
A sixth aspect of the application provides a battery pack comprising the battery module of the fifth aspect of the application.
A seventh aspect of the present application provides an electric device comprising at least one selected from the positive electrode tab of the third aspect of the present application, the secondary battery of the fourth aspect of the present application, the battery module of the fifth aspect of the present application, and the battery pack of the sixth aspect of the present application.
By adopting the technical scheme, the application has the beneficial effects that:
According to the application, polyanion is mixed with lithium sulfide, the p orbit energy of the sulfide ion in the lithium sulfide is reduced by adding the polyanion, so that the covalence of a compound system is reduced, the hybridization between d orbitals and p orbitals is reduced, the share of the transition metal d orbitals in the compound participating in the oxidation-reduction reaction is increased, and meanwhile, the voltage platform of the transition metal is generally higher than that of the sulfide ion, so that the total voltage platform of the system can be improved, the discharge platform of a secondary battery material is improved, and the discharge power of the secondary battery material under low SOC (state of charge) can be improved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
It is apparent that such objects and other objects of the present application will become more apparent from the following detailed description of the preferred embodiments, which is to be read in connection with the accompanying drawings and figures.
The foregoing and other objects, features and advantages of the application will be apparent from the following more particular description of the application, as illustrated in the accompanying drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the application, and are incorporated in and constitute a part of this specification, illustrate the application and together with the embodiments of the application, do not limit the application.
In the drawings, like parts are designated with like reference numerals and are illustrated schematically and are not necessarily drawn to scale.
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only one or several embodiments of the application, and that other drawings can be obtained according to such drawings without inventive effort to a person skilled in the art.
FIG. 1 is a SEM image of sulfides according to some embodiments of the application;
FIG. 2 is a sulfide mechanism diagram of some embodiments of the application;
Fig. 3 is a schematic structural view of a secondary battery according to some embodiments of the present application;
Fig. 4 is a structural exploded view of a secondary battery according to some embodiments of the present application;
Fig. 5 is a schematic view illustrating a structure of a battery module according to some embodiments of the present application;
Fig. 6 is a schematic structural view of a battery pack according to some embodiments of the present application;
Fig. 7 is a structural exploded view of a battery pack according to some embodiments of the present application;
fig. 8 is a schematic structural diagram of an electric device according to some embodiments of the present application.
The main reference numerals illustrate:
1, a battery pack;
2, upper box body;
3, lower box body;
4, a battery module;
5a secondary battery;
51 case, 52 electrode assembly 52, 53 top cap assembly;
and 6, an electric device.
Detailed Description
Hereinafter, embodiments of the negative electrode active material, the method for preparing the same, the negative electrode tab, the secondary battery, the battery module, the battery pack, and the power consumption device of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. Which is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges may be defined in this way as either inclusive or exclusive of the endpoints, and any combination may be made, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if minimum range values 1 and 2 are listed, and if maximum range values 3,4, and 5 are listed, then the following ranges are all contemplated as 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
In the description of embodiments of the present application, the technical terms "first," "second," and the like are used merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, a particular order or a primary or secondary relationship. In the description of the embodiments of the present application, the meaning of "plurality" is two or more unless explicitly defined otherwise.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing the association object, and means that there may be three relationships, for example, a and/or B, and that there may be three cases where a exists alone, while a and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the associated object is an "or" relationship. The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either condition satisfies the condition "A or B" that A is true (or present) and B is false (or absent), that A is false (or absent) and B is true (or present), or that both A and B are true (or present).
In the description of the embodiments of the present application, the term "plurality" means two or more (including two), and similarly, "plural sets" means two or more (including two), and "plural sheets" means two or more (including two).
In the description of the embodiments of the present application, the orientation or positional relationship indicated by the technical terms "center", "longitudinal", "transverse", "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "upper", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. are based on the orientation or positional relationship shown in the drawings, merely for convenience of description and simplification of the description of the embodiments of the present application, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the embodiments of the present application.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The exhaustion of energy resources has led to a significant development of new energy storage devices. Secondary batteries have high energy density, high capacity, good cycle stability and environmental protection characteristics, and thus have been attracting attention.
Currently, the application of secondary batteries is more widespread in view of the development of market situation. The secondary battery is widely used not only in energy storage power supply systems such as hydraulic power, thermal power, wind power and solar power stations, but also in electric vehicles such as electric bicycles, electric motorcycles and electric automobiles, as well as in a plurality of fields such as military equipment and aerospace. With the continuous expansion of the application field of secondary batteries, the market demand thereof is also continuously expanding.
The inventors of the present application have noted that the low discharge plateau of the existing positive electrode material results in failure to normally exert the discharge power performance at low SOC of the secondary battery. The inventors of the present application tried to dope the lithium sulfide with the existing positive electrode material, but the lithium sulfide discharge plateau was low, and although the first charge and discharge efficiency of the battery could be improved to some extent, the discharge power performance of the secondary battery at low SOC could not be improved.
Based on the above-mentioned considerations, in order to improve the discharge power performance of the secondary battery at low SOC, the present inventors have found that the doping of the polyanion into the lithium sulfur compound can greatly improve the discharge power performance of the secondary battery at low SOC by experimental screening of the composition, the proportion, the elements, and the like of the positive electrode material.
Referring to fig. 1-2, fig. 1 is an SEM image of sulfide according to some embodiments of the application, and fig. 2 is a sulfide mechanism diagram according to some embodiments of the application.
According to some embodiments of the present application, there is provided a positive electrode material comprising an oxygen-containing compound of lithium and a polyanion-containing lithium sulfide, the polyanion-containing lithium sulfide being a compound represented by formula I:
LiMS (2-x)(XOm)x A I
Wherein 0< X <2,0< m < 4;M > is selected from at least one of iron (Fe), vanadium (V), niobium (Nb), zirconium (Zr) and manganese (Mn), and X is selected from at least one of phosphorus (P), silicon (Si), sulfur (S), arsenic (As), molybdenum (Mo), tungsten (W) and boron (B).
The oxygen-containing compound of lithium refers to a compound of lithium containing an oxygen element, which includes, but is not limited to, lithium-metal oxides, lithium transition metal oxides, lithium-containing salts, and the like.
Referring again to fig. 1, the lithium sulfide containing a polyanion refers to a compound formed by lithium and sulfur, and the compound has an anion capable of undergoing an ionic polymerization reaction. Wherein polyanion refers to an anion capable of undergoing ionic polymerization, the monomer initiating polymerization is an anion, that is, the reactive moiety at the end of the growing polymer chain is an anion which should be stable, must be capable of chain extension and not isomerize to a stable structure, and lithium sulfide refers to a class of compounds formed by lithium and sulfur.
Therefore, the application mixes polyanion with lithium sulfide, the addition of polyanion reduces p orbit energy of sulfur ion in lithium sulfide, so that the covalence of a compound system is reduced, hybridization between d orbit and p orbit is reduced, the share of d orbit of transition metal in the compound participating in oxidation reduction reaction is increased, meanwhile, the voltage platform of transition metal is generally higher than that of sulfur ion, thus the total voltage platform of the system can be improved, the discharging platform of secondary battery material is improved, and the discharging power of the secondary battery material under low SOC is improved.
In some embodiments, the mass percent of the polyanion-containing lithium sulfide is optionally 3% -10%, alternatively 3% -5%, based on the total mass of the cathode material.
If the mass percentage of the lithium sulfide containing the polyanion is lower than 3%, namely the polyanion (anion capable of carrying out ionic polymerization reaction) in the lithium sulfide is too small, so that the ionic polymerization reaction of the lithium sulfide is incomplete, the p-orbital energy of the sulfide ion in the lithium sulfide cannot be reduced, and the covalent nature in a compound system cannot be reduced, if the mass percentage of the lithium sulfide containing the polyanion is higher than 10%, namely the polyanion (anion capable of carrying out ionic polymerization reaction) in the lithium sulfide is too much, the ionic polymerization reaction of the lithium sulfide reaches saturation, the p-orbital energy of the sulfide ion in the lithium sulfide is too low, so that the influence between the d-orbital and the p-orbital is influenced.
Alternatively, the mass percent of lithium sulfide containing a polyanion is 10%, 9%, 7%, 6%, 5%, 4%, 3%, or a value thereof within a range obtained by combining any two values described above.
Further, the mass percent of the polyanion-containing lithium sulfide is 5%, 4.9%, 4.8%, 4.7%, 4.6%, 4.5%, 4.4%, 4.3%, 4.2%, 4.1%, 3% or a value thereof in a range obtained by combining any two values.
In some embodiments, optionally, the specific surface area of the positive electrode material is 3.5m 2/g～7m2/g. The specific surface area refers to the total area of the material per unit mass, the unit is m 2/g, and generally refers to the specific surface area of the solid material, such as powder, fiber, granule, sheet, block, etc., in other words, the specific surface area is the ratio of area to volume. The application enables the secondary battery to greatly improve the discharge power performance at low SOC by reasonably controlling the specific surface area of the positive electrode material, namely the particle size of the positive electrode material.
Alternatively, the specific surface area of the positive electrode material is 7m2/g、6.5m2/g、6.0m2/g、5.5m2/g、5.0m2/g、4.5m2/g、4.0m2/g、3.5m2/g or the value thereof is within a range obtained by combining any two values described above.
Further, the specific surface area of the positive electrode material is 5m2/g、5.9m2/g、5.8m2/g、5.7m2/g、5.6m2/g、5.5m2/g、5.4m2/g、5.3m2/g、5.2m2/g、5.1m2/g、5.0m2/g、4.9m2/g、4.8m2/g、4.7m2/g、4.6m2/g、4.5m2/g、4.4m2/g、4.3m2/g、4.2m2/g、4.1m2/g、4.0m2/g、3.9m2/g、3.8m2/g、3.7m2/g、3.6m2/g、3.5m2/g or the numerical value thereof is within a range obtained by combining any two numerical values.
In some embodiments, optionally, the lithium-containing oxygen compound comprises a lithium transition metal oxide and/or an olivine structured lithium-containing phosphate. Specifically, the lithium oxygen-containing compound may include only a lithium transition metal oxide, may include only an olivine-structured lithium-containing phosphate, and may include both a lithium transition metal oxide and an olivine-structured lithium-containing phosphate.
Lithium transition metal oxide refers to a material comprising lithium, transition metal, and oxide.
Transition metals refer to a series of metallic elements in the d region of the periodic table, also known as transition elements, which region includes elements of a total of ten groups from 3 to 12, but does not include the inner transition element in the f region.
The olivine structured lithium-containing phosphate refers to a lithium-containing phosphate having an ordered olivine structure. Wherein, the chemical formula of the lithium-containing phosphate is LIMPO 4, and M is manganese (Mn), cobalt (Co) and nickel (Ni).
Further, the lithium transition metal oxide is at least one selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide and modified compounds thereof.
Further, the olivine-structured lithium-containing phosphate is at least one selected from the group consisting of lithium iron phosphate, a composite of lithium iron phosphate and carbon, lithium manganese phosphate, a composite of lithium manganese phosphate and carbon, lithium manganese phosphate, and a composite of lithium manganese phosphate and carbon.
According to the application, the lithium-containing phosphate with a lithium transition metal oxide and/or olivine structure is added, so that the share of transition metal is increased, the share of d orbits of the transition metal in the anode material participating in oxidation-reduction reaction is ensured to be enough, and the voltage platform of the transition metal is generally higher than that of sulfur ions, so that the total voltage platform of the system is greatly improved, and the discharge power performance of the secondary battery under low SOC is improved.
According to some embodiments of the present application, there is provided a method of preparing a positive electrode material, comprising the steps of:
Providing a mixture of lithium sulfide (Li 2 S), metal M, sulfur powder and Li 2XOm, performing ball milling, screening and sintering to obtain lithium sulfide containing polyanion, and mixing the lithium sulfide containing polyanion with an oxygen-containing compound of lithium to obtain a positive electrode material;
wherein the positive electrode material is a polyanion-containing lithium sulfide having the formula I:
LiMS (2-x)(XOm)x A I
0< X <2,0< m < 4;M > is selected from at least one of iron (Fe), vanadium (V), niobium (Nb), zirconium (Zr) and manganese (Mn), and X is selected from at least one of phosphorus (P), silicon (Si), sulfur (S), arsenic (As), molybdenum (Mo), tungsten (W) and boron (B).
The positive electrode material is obtained by mixing lithium sulfide (Li 2 S), metal M, sulfur powder and Li 2XOm in a certain proportion, performing ball milling, screening and sintering to obtain lithium sulfide containing polyanion, and mixing the lithium sulfide containing polyanion and an oxygen-containing compound of lithium in a certain proportion.
According to the application, the polyanion is mixed with the lithium sulfide, and the p orbit energy of the sulfide ions in the lithium sulfide is reduced due to the addition of the polyanion, so that the covalency of a compound system is reduced, the hybridization between d orbits and p orbits is reduced, the share of the transition metal d orbits in the compound participating in the oxidation-reduction reaction is increased, and meanwhile, the voltage platform of the transition metal is generally higher than that of the sulfide ions, so that the total voltage platform of the system can be improved, the discharge platform of the secondary battery material is improved, and the discharge power of the secondary battery material under low SOC is improved.
In some embodiments, optionally, in the ball milling step, the ball milling time is 24-48 h, the ball milling rotation speed is 500-800 r, and the ball-to-material ratio is 50:1-100:1. According to the application, through reasonably setting the ball milling ratio, the ball milling rotating speed and the ball milling time, lithium sulfide (Li 2 S), metal M, sulfur powder and Li 2XOm are mixed more uniformly, so that polyanion can be combined with lithium sulfide more deeply, and a good bedding is provided for the subsequent action of polyanion.
According to some embodiments of the present application, there is provided a positive electrode sheet comprising the positive electrode material of the first aspect of the present application or a positive electrode material produced by the method for producing a positive electrode material of the second aspect of the present application.
According to the application, lithium sulfide (Li 2 S), metal M, sulfur powder and Li 2XOm are mixed according to a certain proportion, and then ball milling, screening and sintering are carried out to obtain the lithium sulfide containing polyanion, and then the lithium sulfide containing polyanion and the oxygen-containing compound of lithium are mixed according to a certain proportion to obtain the anode material.
According to the application, the polyanion is mixed with the lithium sulfide, and the p orbit energy of the sulfide ions in the lithium sulfide is reduced due to the addition of the polyanion, so that the covalency of a compound system is reduced, the hybridization between d orbits and p orbits is reduced, the share of the transition metal d orbits in the compound participating in the oxidation-reduction reaction is increased, and meanwhile, the voltage platform of the transition metal is generally higher than that of the sulfide ions, so that the total voltage platform of the system can be improved, the discharge platform of the secondary battery material is improved, and the discharge power of the secondary battery material under low SOC is improved.
The positive electrode sheet of the application has the beneficial effects of the positive electrode material as well, because the positive electrode sheet comprises the positive electrode material of the first aspect of the application or the positive electrode material prepared by the preparation method of the second aspect of the application.
Referring to fig. 3 to 4, fig. 3 is a schematic structural view of a secondary battery according to some embodiments of the present application, and fig. 4 is an exploded structural view of a secondary battery according to some embodiments of the present application.
According to some embodiments of the present application, the present application provides a secondary battery 5.
In general, the secondary battery 5 includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ Positive electrode sheet ]
The positive electrode plate comprises a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, wherein the positive electrode film layer comprises the positive electrode material of the first aspect of the application.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode material may include at least one of an olivine structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode material may be used. These positive electrode materials may be used alone or in combination of two or more. Wherein, examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (e.g., liCoO 2), lithium nickel oxide (e.g., liNiO 2), lithium manganese oxide (e.g., liMnO 2、LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi 1/3Co1/3Mn1/3O2 (which may also be abbreviated as NCM 333)、LiNi0.5Co0.2Mn0.3O2 (which may also be abbreviated as NCM 523)、LiNi0.5Co0.25Mn0.25O2 (which may also be abbreviated as NCM 211)、LiNi0.6Co0.2Mn0.2O2 (which may also be abbreviated as NCM 622)、LiNi0.8Co0.1Mn0.1O2 (which may also be abbreviated as NCM 811)), lithium nickel manganese oxide (which may also be abbreviated as NCM 333)、LiNi0.5Co0.2Mn0.3O2 (which may also be abbreviated as NCM 42 examples of the olivine structured lithium-containing phosphate may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO 4 (which may also be abbreviated as LFP)), a composite of lithium iron phosphate and carbon, a composite of lithium manganese phosphate (such as LiMnPO 4), a composite of lithium manganese phosphate and carbon, a composite of lithium manganese phosphate, lithium iron phosphate, and a composite of lithium manganese phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by dispersing the above components for preparing the positive electrode sheet, such as a positive electrode material, a conductive agent, a binder, and any other components, in a solvent (e.g., N-methylpyrrolidone) to form a positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and performing processes such as drying, cold pressing, and the like to obtain the positive electrode sheet.
[ Negative electrode plate ]
The negative pole piece comprises a negative pole current collector and a negative pole film layer arranged on at least one surface of the negative pole current collector, wherein the negative pole film layer comprises a negative pole material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative electrode material may employ a negative electrode material for a battery, which is well known in the art. As an example, the negative electrode material may include at least one of artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based material, tin-based material, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode material may be used. These negative electrode materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet may be prepared by dispersing the above components for preparing the negative electrode sheet, such as the negative electrode material, the conductive agent, the binder, and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, and performing processes such as drying, cold pressing, and the like to obtain the negative electrode sheet.
[ Electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ Isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
[ Secondary Battery 5]
And assembling the positive electrode plate and the negative electrode plate into a battery core, and performing the procedures of liquid injection, formation, aging, K measurement, capacity test and the like to obtain the secondary battery 5.
In some embodiments, secondary battery 5 may include an outer package. The outer package may be used to encapsulate the electrode assembly 52 and electrolyte described above.
In some embodiments, the exterior package of the secondary battery 5 may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The exterior package of the secondary battery 5 may be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the secondary battery 5 is not particularly limited in the present application, and may be cylindrical, square, or any other shape.
In some embodiments, the overpack may include a housing 51 and a cap assembly 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing has an opening in communication with the receiving chamber, and the cap assembly 53 can be capped at the opening to close the receiving chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is packaged in the receiving chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements.
Referring to fig. 5, fig. 5 is a schematic view illustrating a structure of a battery module according to some embodiments of the present application.
According to some embodiments of the present application, the present application provides a battery module 4. The battery module 4 includes the secondary battery 5 provided by the present application. The number of secondary batteries 5 included in the battery module 4 may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery module 4.
In the battery module 4, the plurality of secondary batteries 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of secondary batteries 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a case having an accommodating space in which the plurality of secondary batteries 5 are accommodated.
Referring to fig. 6 to 7, fig. 6 is a schematic structural view of a battery pack according to some embodiments of the present application, and fig. 7 is an exploded structural view of a battery pack according to some embodiments of the present application.
According to some embodiments of the present application, the present application provides a battery pack 1. The battery pack 1 includes the battery module 4 provided by the present application. The number of the battery modules 4 included in the battery pack 1 may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack 1.
A battery box and a plurality of battery modules provided in the battery box may be included in the battery pack 1. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3, and a closed space for accommodating the battery module 4 is formed. The plurality of battery modules 4 may be arranged in the battery box in any manner.
Referring to fig. 8, fig. 8 is a schematic structural diagram of an electric device according to some embodiments of the present application.
According to some embodiments of the application, the application provides an electrical device 6. The power consumption device 6 comprises at least one selected from the positive electrode plate provided by the application, the secondary battery 5 provided by the application, the battery module 4 provided by the application and the battery pack 1 provided by the application. The secondary battery 5, the battery module 4, and the battery pack 1 may be used as a power source of the electric device 6, or may be used as an energy storage unit of the electric device 6. The power utilization device 6 may include mobile equipment (e.g., cellular phone, notebook computer, etc.), electric vehicles (e.g., electric-only vehicle, hybrid electric vehicle, plug-in hybrid electric vehicle, electric bicycle, electric scooter, electric golf cart, electric truck, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electric power consumption device 6, the secondary battery 5, the battery module 4, or the battery pack 1 may be selected according to the use requirements thereof.
The electric device 6 is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery 5 by the power consuming device 6, the battery pack 1 or the battery module 4 may be employed.
In some embodiments, the power consumption device 6 may be a mobile phone, a tablet computer, a notebook computer, or the like. The power utilization device 6 is required to be generally thin and lightweight, and the secondary battery 5 can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The positive electrode material includes a lithium oxygen-containing compound including a lithium transition metal oxide and a lithium-containing phosphate of an olivine structure, and a polyanion-containing lithium sulfide, which is LiTiS (SO 4).
Wherein the mass percentage of the lithium sulfide containing polyanion is 6.5% based on the total mass of the positive electrode material, and the specific surface area of the positive electrode material is 5m 2/g.
[ Method for producing Positive electrode Material ]
Providing a mixture of Li 2 S, metal M, sulfur powder and Li 2XOm, performing ball milling (the ball milling time is 36h, the ball milling rotating speed is 650r, the ball material ratio is 75:1), screening, sintering to obtain lithium sulfide containing polyanion, and mixing the lithium sulfide containing polyanion with an oxygen-containing compound of lithium to obtain the cathode material.
[ Method for producing Secondary Battery ]
Fully stirring and uniformly mixing the anode material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) in an N-methylpyrrolidone solvent according to a weight ratio of 96:3:1, coating the mixture on an aluminum foil, drying and cold pressing to obtain an anode sheet;
fully stirring and uniformly mixing artificial graphite serving as a negative electrode material, a conductive agent Super P, a binder styrene-butadiene rubber (SBR) and a thickener sodium methyl cellulose (CMC) in a deionized water solvent system according to a weight ratio of 97:0.5:1.5:1, coating the mixture on a copper foil, drying, and cold pressing to obtain a negative electrode plate;
The isolating film is made of polyvinylidene fluoride;
And sequentially overlapping the positive electrode plate, the isolating film and the negative electrode plate, so that the isolating film is positioned between the positive electrode and the negative electrode to play a role in isolation, and winding to obtain the bare cell. And placing the bare cell in a corresponding aluminum shell, injecting electrolyte and packaging to obtain the secondary battery.
Example 2
This example differs from example 1 in that the lithium sulfide containing a polyanion is LiTiS (PO 4).
Example 3
This example differs from example 1 in that the lithium sulfide containing a polyanion is LiTiS (BO 3).
Example 4
This example differs from example 1 in that the lithium sulfide containing the polyanion is LiVS (SO 4).
Example 5
This example differs from example 1 in that the lithium sulfide containing the polyanion is LiZrS (SO 4).
Example 6
This example differs from example 1 in that the mass percentage of lithium sulfide containing a polyanion is 3.0% based on the total mass of the positive electrode material.
Example 7
This example differs from example 1 in that the mass percentage of lithium sulfide containing a polyanion is 10.0% based on the total mass of the positive electrode material.
Example 8
This example differs from example 1 in that the specific surface area of the positive electrode material is 3.5m 2/g.
Example 9
The difference between this example and example 1 is that the specific surface area of the positive electrode material is 7m 2/g.
Comparative example 1
This comparative example is different from example 1-1 in that the positive electrode material includes an oxygen-containing compound of lithium including a lithium transition metal oxide and a lithium-containing phosphate of olivine structure and a lithium sulfide of Li2S.
Comparative example 2
This comparative example differs from example 1-1 in that the positive electrode material includes an oxygen-containing compound of lithium including a lithium transition metal oxide and a lithium-containing phosphate of an olivine structure.
[ Secondary Battery Performance test ]
Testing of Secondary Battery Power Performance
Charging and discharging the secondary battery for a certain time, and then calculating a DCR (Direct Current Resistance ) value, wherein the value is calculated according to the following calculation formula:
RDCR Discharge of electric power (I1,t1)＝|V1-V2|/I1;
RDCR charging method (I2,t2)＝|V4-V3|/I2;
Wherein I 1 is the discharge current value, I 2 is the charge current value, t 1 is the discharge duration, t 2 is the charge duration, V 1 is the voltage value for starting the discharge, V 2 is the voltage value for ending the discharge, V 3 is the voltage value for starting the charge, and V 4 is the voltage value for ending the charge.
The positive electrode material-related parameters and battery performance test data of examples and comparative examples are shown in table 1.
Table 1 examples and comparative examples positive electrode material related parameters and secondary battery performance test data
[ Data analysis ]
As is clear from table 1, the DCR value was calculated by charging and discharging the secondary battery for a certain period of time. Wherein,
The positive electrode materials in the secondary batteries of comparative examples 1 and 2 did not add polyanion, resulting in no decrease in p-orbital energy of the sulfide ion in lithium sulfide, no decrease in covalent nature of the compound system, much hybridization between d-orbitals and p-orbitals, and a small share of d-orbitals of transition metal in the compound involved in redox reaction, so that DCR at 10% soc was as high as 0.72, far higher than examples 1 to 9.
The positive electrode materials in the secondary batteries of examples 1 to 9 mix the polyanion with lithium sulfide, and since the addition of the polyanion reduces the p-orbital energy of the sulfur ion in the lithium sulfide, the covalency of the compound system is reduced, the hybridization between d-orbitals and p-orbitals is reduced, the share of the transition metal d-orbitals in the compound participating in the oxidation-reduction reaction is increased, so that the DCR value at 10% SOC is between 0.46 and 0.61, i.e., the discharge power performance of the secondary batteries of examples 1 to 9 at low SOC is greatly improved.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (12)
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| CN103367791A (en) * | 2013-07-15 | 2013-10-23 | 中国科学院化学研究所 | Novel lithium ion battery |
| CN105118957A (en) * | 2015-07-04 | 2015-12-02 | 广东烛光新能源科技有限公司 | A lithium-sulfur battery electrode, a lithium-sulfur battery containing the electrode, and a preparation method thereof |
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| WO2013161982A1 (en) * | 2012-04-27 | 2013-10-31 | 株式会社村田製作所 | Solid-state battery, and method for producing same |
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| CN105118957A (en) * | 2015-07-04 | 2015-12-02 | 广东烛光新能源科技有限公司 | A lithium-sulfur battery electrode, a lithium-sulfur battery containing the electrode, and a preparation method thereof |
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