Patent Application
20230361272
The present application relates to the technical field of batteries, and in particular to a positive electrode plate, a secondary battery and a power consuming device.
In recent years, with the increasing application range, secondary batteries are widely used in energy storage power systems such as hydraulic power, thermal power, wind power and solar power stations, as well as many fields such as electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, and aerospace. Due to the great development of secondary batteries, higher requirements have also been placed on the secondary batteries in terms of energy density, cycling performance, etc.
In the related art, a conductive undercoat layer is provided between the active material of the positive electrode plate and the current collector to improve one or more performances of the secondary battery.
In order to further improve the performance of the battery, a better positive electrode plate is needed.
In view of the above consideration, the present application provides a new positive electrode plate, a secondary battery and a power consuming device. The new positive electrode plate comprises a new positive electrode active material and a new conductive undercoat layer, which will be described respectively below.
In a first aspect, the present application provides a positive electrode plate, comprising a positive electrode current collector, a positive electrode film layer provided on at least one surface of the positive electrode current collector, and a conductive undercoat layer between the positive electrode current collector and the positive electrode film layer, wherein
the positive electrode film layer comprises a positive electrode active material of a chemical formula of LiaAxMn1-yByP1-zCzO4-nDn, wherein A comprises one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W, B comprises one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge, C comprises one or more elements selected from B (boron), S, Si and N, and D comprises one or more elements selected from S, F, Cl and Br; and a is selected from a range of 0.9 to 1.1, x is selected from a range of 0.001 to 0.1, y is selected from a range of 0.001 to 0.5, z is selected from a range of 0.001 to 0.1, and n is selected from a range of 0.001 to 0.1; the positive electrode active material is electrically neutral; and
In some embodiments, based on the total mass of the first polymer,
In some embodiments, M3/(M2+M3) is 0%-5%, optionally 0.001%-1%.
In some embodiments, the first polymer is one or more selected from hydrogenated nitrile rubbers, and hydrogenated carboxylated nitrile rubbers; and/or
In some embodiments, the first water-based binder includes one or more selected from a water-based polyacrylic resin and a derivative thereof, a water-based amino-modified polypropylene resin and a derivative thereof, a polyvinyl alcohol and a derivative thereof, optionally a water-based acrylic acid-acrylate copolymer; and/or
In some embodiments, the first conductive agent includes one or more selected from superconductive carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers, optionally one or more selected from carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, based on the total mass of the conductive undercoat layer,
In some embodiments, the conductive undercoat layer has a thickness of 1 μm-20 μm, optionally 3 μm-10 μm.
In some embodiments, the positive electrode film layer further includes one or more selected from an infiltration agent and a dispersant, optionally, the positive electrode film layer further includes both an infiltration agent and a dispersant.
In some embodiments, the infiltration agent has a surface tension of 20 mN/m-40 mN/m, optionally, the infiltration agent includes at least one of the functional groups of: —CN, —NH2, —NH—, —N—, —OH, —COO—, —C(═O)—O—C(═O)—.
In some embodiments, the infiltration agent includes one or more selected from small molecule organic solvents and low molecular weight polymers.
In some embodiments, the small molecule organic solvent includes one or more selected from an alcohol amine compound, an alcohol compound, and a nitrile compound, and optionally, the alcohol amine compound has a number of carbon atom of 1-16, optionally 2-6.
In some embodiments, the low molecular weight polymer includes one or more selected from a maleic anhydride-styrene copolymer, polyvinylpyrrolidone, and polysiloxane, and optionally, the low molecular weight polymer has a weight-average molecular weight of not more than 6000, optionally 3000-6000.
In some embodiments, the dispersant includes a second polymer, and the second polymer comprises:
In some embodiments, based on the total mass of the second polymer,
In some embodiments, M7/(M6+M7) is 0%-5%, optionally 0.001%-1%.
In some embodiments, the second polymer is a hydrogenated nitrile rubber; and/or
In some embodiments, based on the total mass of the positive electrode film layer,
In some embodiments, Y1/Y2 is 0.05-20, optionally 0.1-1, further 0.3-0.8.
In some embodiments, in the positive electrode plate, the mass ratio of the first polymer to the second polymer is 1.5-5, optionally 2-3.
In some embodiments, A, C and D are each independently any element in the respective ranges, and B is at least two elements in the range thereof;
In some embodiments, x is selected from a range of 0.001 to 0.005; and/or
In some embodiments, (1-y):y is in a range of 1 to 4, optionally a range of 1.5 to 3, and a: x is in a range of 9 to 1100, optionally a range of 190 to 998.
In some embodiments, the lattice change rate of the positive electrode active material is not more than 8%, optionally not more than 4%.
In some embodiments, the Li/Mn antisite defect concentration of the positive electrode active material is 2% or less, optionally 0.5% or less.
In some embodiments, the surface oxygen valence state of the positive electrode active material is not more than −1.82, optionally −1.89 to −1.98.
In some embodiments, the compacted density of the positive electrode active material under 3 T is no less than 2.0 g/cm3, optionally no less than 2.2 g/cm3.
In some embodiments, the surface of the positive electrode active material is coated with carbon.
In some embodiments, the positive electrode active material has a specific surface area of 15 m2/g-25 m2/g, and the coating weight on one side of the positive electrode current collector is 20 mg/cm2-40 mg/cm2. When the positive electrode active material has a specific surface area of 15 m2/g-25 m2/g, and the coating weight on one side of the positive electrode current collector is 20 mg/cm2-40 mg/cm2, the film peeling phenomenon easily occurs during the coating process. In the present application, a new conductive undercoat layer is used to increase the bonding strength between the positive electrode active material layer and the current collector.
In a second aspect, the present application provides a secondary battery, including the positive electrode plate described in any one of the above embodiments.
In a third aspect, the present application provides a power consuming device, comprising the above secondary battery.
As a positive electrode active material of a lithium ion secondary battery, lithium manganese phosphate has a disadvantage of a poor rate performance when compared with other positive electrode active materials, and this problem is now usually solved by means of coating or doping, etc. However, it is still desirable to further improve the rate performance, cycle performance, high-temperature stability and the like of the lithium manganese phosphate positive electrode active material.
Through repeated studies on the effects of doping lithium manganese phosphate at Li, Mn, P and O-sites with various elements, the inventors of the present application have found that by use of simultaneous doping at the above four sites with specific amounts of specific elements, a markedly improved rate performance and improved cycle performance and/or high-temperature performance can be obtained, thereby obtaining an improved lithium manganese phosphate positive electrode active material.
The positive electrode active material of the present application can, for example, be used in a lithium ion secondary battery.
Specifically, in a fourth aspect, the present application provides a positive electrode active material of a chemical formula of LiaAxMn1-yByP1-zCzO4-nDn,
Unless otherwise stated, in the above chemical formula, when A is a combination of at least two elements, the above definition of the numerical range of x not only represents a definition of the stoichiometric number of each element as A, but also represents a definition of the sum of the stoichiometric numbers of the elements as A. For example, when A is a combination of at least two elements A1, A2 . . . An, the stoichiometric numbers x1, x2 . . . xn of A1, A2 . . . An each fall within the numerical range of x defined in the present application, and the sum of x1, x2 . . . xn also falls within this numerical range. Similarly, when B, C and D are each a combination of at least two elements, the definitions of the numerical ranges of the stoichiometric numbers of B, C and D in the present application also have the above meanings.
The positive electrode active material of the present application is obtained by doping a compound LiMnPO4 with elements, wherein A, B, C and D are respectively the elements for doping at Li, Mn, P and O sites of the compound LiMnPO4. Without wishing to be bound by theory, it is now believed that a performance improvement of lithium manganese phosphate is associated with a reduction in the lattice change rate of lithium manganese phosphate in a lithium intercalation/de-intercalation process and a decrease in surface activity. A reduction in the lattice change rate can reduce the difference of lattice constants between two phases at a grain boundary, lower the interface stress and enhance the Li+ transport ability at an interface, thereby improving the rate performance of the positive electrode active material. A high surface activity can easily lead to severe interfacial side reactions, and exacerbates gas production, electrolyte consumption and interface damage, thereby affecting the cycling performance and the like of the battery. In the present application, the lattice change rate is reduced by doping at the sites of Li and Mn. The Mn-position doping also effectively decreases the surface activity, thereby inhibiting the Mn dissolution and the interfacial side reactions between the positive electrode active material and the electrolyte. The P-site doping increases the change rate of the Mn—O bond length and reduces the small-polaron migration barrier of the material, which is beneficial for electronic conductivity. The O-site doping plays a good role in reducing the interfacial side reactions. The P-position and O-position doping also has an effect on the dissolution of Mn of antisite defects and the dynamic performance. Therefore, the doping reduces the antisite effect concentration in the material, improves the dynamic performance and gram capacity of the material, and can also change the particle morphology, thereby increasing the compacted density. The applicant has unexpectedly found that: by doping a compound LiMnPO4 at Li, Mn, P and O-sites with specific amounts of specific elements, a markedly improved rate performance can be obtained while the dissolution of Mn and Mn-position doping element is significantly reduced, thereby obtaining significantly improved cycle performance and/or high-temperature stability; and the gram capacity and compacted density of the material can also be enhanced.
Optionally, A is one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W, B is one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge, C is one or more elements selected from B (boron), S, Si and N, and D is one or more elements selected from S, F, Cl and Br.
In some embodiments, A, C and D are each independently any element in the above respective ranges, and B is at least two elements. Therefore, the composition of the positive electrode active material can be controlled more easily and accurately.
By selecting the Li-site doping element in the above ranges, the lattice change rate in a lithium de-intercalation process can be further reduced, thereby further improving the rate performance of the battery. By selecting the Mn-site doping element in the above ranges, the electronic conductivity can be further increased while the lattice change rate is further reduced, thereby improving the rate performance and gram capacity of the battery. By selecting the P-site doping element in the above ranges, the rate performance of the battery can be further improved. By selecting the O-site doping element in the above ranges, interfacial side reactions can be further alleviated, thereby improving the high-temperature performance of the battery.
In some embodiments, the x is selected from a range of 0.001 to 0.005; and/or, the y is selected from a range of 0.01 to 0.5, optionally a range of 0.25 to 0.5; and/or, the z is selected from a range of 0.001 to 0.005; and/or, the n is selected from a range of 0.001 to 0.005. By selecting the y value in the above ranges, the gram capacity and rate performance of the material can be further improved. By selecting the x value in the above ranges, the dynamic performance of the material can be further improved. By selecting the z value in the above ranges, the rate performance of the secondary battery can be further improved. By selecting the n value in the above ranges, the high-temperature performance of the secondary battery can be further improved.
In some embodiments, the positive electrode active material satisfies that: (1-y):y is in a range of 1 to 4, optionally a range of 1.5 to 3, and a:x is in a range of 9 to 1,100, optionally a range of 190 to 998. Here, y denotes the sum of the stoichiometric numbers of the Mn-site doping elements. When the above conditions are satisfied, the energy density and cycling performance of the positive electrode active material can be further improved.
In some embodiments, the lattice change rate of the positive electrode active material is not more than 8%, optionally not more than 4%. By lowering the lattice change rate, the Li ion transport can be made easier, that is, the Li ions have a stronger migration ability in the material, which is beneficial in improving the rate performance of the secondary battery. The lattice change rate may be measured with a method known in the art, e.g., X-ray diffraction (XRD).
In some embodiments, the Li/Mn antisite defect concentration of the positive electrode active material is not more than 2%, optionally, the Li/Mn antisite defect concentration is not more than 0.5%. The so-called Li/Mn antisite defect means that the sites of Li+ and Mn2+ have been exchanged in the LiMnPO4 lattices. The Li/Mn antisite defect concentration refers to a percentage of the Li+ exchanged with Mn2+ based on the total amount of Li+ in the positive electrode active material. The Mn2+ of antisite defects can hinder the transport of Li+, and a reduction in the Li/Mn antisite defect concentration is beneficial in improving the gram capacity and rate performance of the positive electrode active material. The Li/Mn antisite defect concentration may be measured with a method known in the art, e.g., XRD.
In some embodiments, the surface oxygen valence state of the positive electrode active material is not more than −1.82, optionally −1.89 to −1.98. By lowering the surface oxygen valence state, the interfacial side reactions between the positive electrode active material and an electrolyte can be alleviated, thereby improving the cycling performance and high-temperature stability of the secondary battery. The surface oxygen valence state may be measured with a method known in the art, e.g., electron energy loss spectroscopy (EELS).
In some embodiments, the compacted density of the positive electrode active material under 3 T (ton) is not less than 2.0 g/cm3, optionally not less than 2.2 g/cm3. A higher compacted density indicates a greater weight of the active material per unit volume, and thus, increasing the compacted density is beneficial in increasing the volumetric energy density of a cell. The compacted density may be measured in accordance with GB/T 24533-2009.
In some embodiments, the surface of the positive electrode active material is coated with carbon. Therefore, the electrical conductivity of the positive electrode active material can be improved.
One or more embodiments of the present application have one or more of the following beneficial effects:
Hereinafter, embodiments of a positive electrode active material and a preparation method therefor, a positive electrode plate, a negative electrode plate, a secondary battery, a battery module, a battery pack, and a device of the present application are described in detail and specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed illustrations may be omitted in some instances. For example, there are situations where detailed description of well known items and repeated description of actually identical structures are omitted. This is to prevent the following description from being unnecessarily verbose, and facilitates understanding by those skilled in the art. Moreover, the accompanying drawings and the descriptions below are provided for enabling those skilled in the art to fully understand the present application, rather than limiting the subject matter disclosed in claims.
“Ranges” disclosed in the present application are defined in the form of lower and upper limits, and a given range is defined by selection of a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if the ranges of 60-120 and 80-110 are listed for a particular parameter, it should be understood that the ranges of 60-110 and 80-120 are also contemplated. Additionally, if minimum range values 1 and 2 are listed, and maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless stated otherwise, the numerical range “a-b” denotes an abbreviated representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, the numerical range “0-5” means that all real numbers between “0-5” have been listed herein, and “0-5” is just an abbreviated representation of combinations of these numerical values. In addition, when a parameter is expressed as an integer of ≥2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the like.
All the implementations and optional implementations of the present application can be combined with one another to form new technical solutions, unless otherwise stated.
All technical features and optional technical features of the present application can be combined with one another to form a new technical solution, unless otherwise stated.
Unless otherwise stated, all the steps of the present application can be carried out sequentially or randomly, in some embodiment sequentially. For example, the method including steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, and may also include steps (b) and (a) performed sequentially. For example, reference to “the method may further include step (c)” indicates that step (c) may be added to the method in any order, e.g., the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.
The terms “comprise” and “include” mentioned in the present application are open-ended, unless otherwise stated. For example, “comprise” and “include” may mean that other components not listed may or may not further be comprised or included.
In the present application, the term “or” is inclusive unless otherwise specified. For example, the phrase “A or B” means “A, B, or both A and B”. More specifically, a condition “A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present). In this disclosure, the phrases “at least one of A, B, and C” and “at least one of A, B, or C” both mean only A, only B, only C, or any combination of A, B, and C.
[Secondary Battery]
A secondary battery, also known as a rechargeable battery or an accumulator, refers to a battery of which active materials can be activated by means of charging for reuse of the battery after the battery is discharged.
Generally, the secondary battery comprises a positive electrode plate, a negative electrode plate, a separator and an electrolyte. During a charge/discharge process of the battery, active ions (e.g., lithium ions) are intercalated and de-intercalated back and forth between the positive electrode plate and the negative electrode plate. The separator is provided between the positive electrode plate and the negative electrode plate, and mainly prevents positive and negative electrodes from short-circuiting and enables the active ions to pass through. The electrolyte is provided between the positive electrode plate and the negative electrode plate and mainly functions for active ion conduction.
[Positive Electrode Plate]
In some embodiments, the present application provides a positive electrode plate, comprising a positive electrode current collector, a positive electrode film layer provided on at least one surface of the positive electrode current collector, and a conductive undercoat layer between the positive electrode current collector and the positive electrode film layer, wherein
the positive electrode film layer comprises a positive electrode active material of a chemical formula of LiaAxMn1-yByP1-zCzO4-nDn, wherein A comprises one or more elements selected from Zn, Al, Na, K, Mg, Nb, Mo and W, B comprises one or more elements selected from Ti, V, Zr, Fe, Ni, Mg, Co, Ga, Sn, Sb, Nb and Ge, C comprises one or more elements selected from B (boron), S, Si and N, and D comprises one or more elements selected from S, F, Cl and Br; a is selected from a range of 0.9 to 1.1, x is selected from a range of 0.001 to 0.1, y is selected from a range of 0.001 to 0.5, z is selected from a range of 0.001 to 0.1, and n is selected from a range of 0.001 to 0.1; and the positive electrode active material is electrically neutral; and
In the positive electrode plate based on the above solution, the bonding strength between the positive electrode film layer and the positive electrode current collector is enhanced. Without being limited by theory, during the process of coating the surface of the conductive undercoat layer with the positive electrode active material slurry (containing a solvent of N-methylpyrrolidone, referred to as NMP), the first polymer in the conductive undercoat layer will dissolve again after coming into the contact with the solvent of NMP, so as to interdiffuse with the positive electrode active material slurry, and after curing, the active material layer can be integrated with the undercoat layer, thereby effectively increasing the bonding strength between the positive electrode film layer and the positive electrode current collector.
In some embodiments, the first polymer is a random copolymer.
Nitrile rubber (NBR) is a random copolymer formed by polymerization (such as emulsion polymerization) of acrylonitrile and butadiene monomers, and has a general structure of:
In the nitrile rubber, butadiene (B) and acrylonitrile (A) segments are generally linked by BAB, BBA or ABB, ABA and BBB tridas, but with the increase of acrylonitrile content, there are also AABAA linked in pentad and even as a bulk acrylonitrile polymer. In the nitrile rubber, the sequence distribution of butadiene is mainly in a trans-1,4 structure, and the microstructure thereof depends on the polymerization conditions.
A hydrogenated nitrile rubber (HNBR) refers to the product obtained by hydrogenating the carbon-carbon double bonds on the molecular chain of a nitrile rubber to partial or full saturation. The chemical formula of fully saturated hydrogenated nitrile rubber is as follows:
There are three main methods for the preparation of a hydrogenated nitrile rubber (HNBR): an ethylene-acrylonitrile copolymerization method, an NBR solution hydrogenation method and an NBR emulsion hydrogenation method.
A hydrogenated carboxybutyl rubber (HXNBR) is a polymer formed by copolymerization of nitrile (such as acrylonitrile), a conjugated diene (such as butadiene) and an ester of an unsaturated carboxylic acid, followed by selective hydrogenation of C═C. The so-called hydrogenated carboxyl butyl rubber is based on hydrogenated nitrile rubber, to which a carboxyl group is further introduced.
The ester of an unsaturated carboxylic acids includes, for example, an ester of a α,β-unsaturated monocarboxylic acid. Esters of α,β-unsaturated monocarboxylic acids that can be used are alkyl esters and alkoxyalkyl esters thereof, optionally, alkyl esters of α,β-unsaturated monocarboxylic acids, such as C1-C18 alkyl esters, optionally alkyl esters of acrylic acid or methacrylic acid, such as C1-C18 alkyl esters, specifically for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; and also optionally alkoxyalkyl esters of α,β-unsaturated monocarboxylic acids, optionally alkoxyalkyl esters of acrylic acid or methacrylic acid, e.g., C2-C12-alkoxyalkyl esters of acrylic acid or methacrylic acid, and further optionally methoxymethyl acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and methoxyethyl (meth)acrylate. Mixtures of alkyl esters such as those described above with alkoxyalkyl esters such as those described above may also be used. Hydroxyalkyl acrylate and hydroxyalkyl methacrylate in which the number of carbon atoms in the hydroxyalkyl group is 1-12 can also be used, for example 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl acrylate. Likewise, epoxy-containing esters such as glycidyl methacrylate may be used. Cyanoalkyl acrylates and cyanoalkyl methacrylates with 2-12 C atoms in the cyanoalkyl can also be used, for example α-cyanoethyl acrylate, β-cyanoethyl acrylate and cyanobutyl methacrylate. Acrylates or methacrylates containing fluorine-substituted benzyl groups can also be used, for example, fluorobenzyl acrylate and fluorobenzyl methacrylate. Acrylates and methacrylates containing fluoroalkyl groups can also be used, for example trifluoroethyl acrylate and tetrafluoropropyl methacrylate. Amino group-containing α,β-unsaturated carboxylic acid esters such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate can also be used.
In some embodiments, based on the total mass of the first polymer,
In some embodiments, based on the total mass of the first polymer,
The mass percentage content of the first monomeric unit is M1, and M1 is 10%-55%, optionally 10%-15%, 15%-20%, 20%-25%, 25%-30%, 30%-35%, 35%-40%, 40%-45%, 45%-50% or 50%-55%; and/or
In some embodiments, M3/(M2+M3) is 0%-5%, optionally 0.001%-1%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, M3/(M2+M3) is 0.01%-1%, 1%-2%, 2%-3%, 3%-4% or 4%-5%.
In some embodiments, the first polymer is one or more selected from hydrogenated nitrile rubbers, and hydrogenated carboxylated nitrile rubbers; and/or
In some embodiments, the first polymer has a weight-average molecular weight of 100,000-300,000, 300,000-500,000, 500,000-700,000, 700,000-900,000, 900,000-1,100,000, 1,100,000-1,300,000 or 1,300,000-1,500,000.
In some embodiments, the first water-based binder includes one or more selected from a water-based polyacrylic resin and a derivative thereof, a water-based amino-modified polypropylene resin and a derivative thereof, a polyvinyl alcohol and a derivative thereof, optionally a water-based acrylic acid-acrylate copolymer; and/or
In some embodiments, the weight-average molecular weight of the first water-based binder is 100,000-300,000, 300,000-500,000, 500,000-700,000, 700,000-900,000, 900,000-1,100,000, or 1,100,000-1,300,000.
In some embodiments, the first conductive agent includes one or more selected from superconductive carbon, conductive graphite, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers, optionally one or more selected from carbon nanotubes, graphene, and carbon nanofibers. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, based on the total mass of the conductive undercoat layer,
In some embodiments, the conductive undercoat layer has a thickness of 1 m-20 m, optionally 3 m-10 m. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the positive electrode film layer further includes one or more selected from an infiltration agent and a dispersant, optionally, the positive electrode film layer further includes both an infiltration agent and a dispersant. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the infiltration agent has a surface tension of 20 mN/m-40 mN/m, optionally, the infiltration agent includes at least one of the functional groups of: —CN, —NH2, —NH—, —N—, —OH, —COO—, —C(═O)—O—C(═O)—.
In some embodiments, the surface tension can be measured using the Wilhelmy Plate Method. For the specific test steps, reference can be made to general standards in the field, such as GBT/22237-2008 Surface Active Agents-Determination of Surface Tension, such as ASTM D1331-14. Standard Test Methods for Surface and Interfacial Tension of Solutions of Paints Solvents Solutions of Surface-Active Agents and Related Materials.
In some embodiments, the infiltration agent includes one or more selected from small molecule organic solvents and low molecular weight polymers. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the small molecule organic solvent includes one or more selected from an alcohol amine compound, an alcohol compound, and a nitrile compound, and optionally, the alcohol amine compound has a number of carbon atom of 1-16, optionally 2-6;
In some embodiments, the low molecular weight polymer includes one or more selected from a maleic anhydride-styrene copolymer, polyvinylpyrrolidone, and polysiloxane, and optionally, the low molecular weight polymer has a weight-average molecular weight of not more than 6000, optionally 3000-6000. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the dispersant includes a second polymer, and the second polymer comprises:
The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, based on the total mass of the second polymer,
In some embodiments, based on the total mass of the second polymer,
In some embodiments, M7/(M6+M7) is 0%-5%, optionally 0.001%-1%.
In some embodiments, the second polymer is a hydrogenated nitrile rubber; and/or
In some embodiments, based on the total mass of the positive electrode film layer,
In some embodiments, Y1/Y2 is 0.05-20, optionally 0.1-1, further 0.3-0.8. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, in the positive electrode plate, the mass ratio of the first polymer to the second polymer is 1.5-5, optionally 2-3. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, A, C and D are each independently any element in the respective ranges, and B is at least two elements in the range thereof;
In some embodiments, x is selected from a range of 0.001 to 0.005; and/or
In some embodiments, (1-y):y is in a range of 1 to 4, optionally a range of 1.5 to 3, and a:x is in a range of 9 to 1,100, optionally a range of 190 to 998. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the lattice change rate of the positive electrode active material is not more than 8%, optionally not more than 4%. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the Li/Mn antisite defect concentration of the positive electrode active material is 2% or less, optionally 0.5% or less. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the surface oxygen valence state of the positive electrode active material is not more than −1.82, optionally −1.89 to −1.98. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the compacted density of the positive electrode active material under 3 T is not less than 2.0 g/cm3, optionally not less than 2.2 g/cm3. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, the surface of the positive electrode active material is coated with carbon. The positive electrode plate based on this solution is used in secondary batteries, where one or more of the properties of the secondary battery are significantly improved.
In some embodiments, a method for preparing a positive electrode active material comprises the following steps:
In some embodiments, the stirring of step (1) is carried out at a temperature in a range of 60° C. to 120° C., and/or,
In some embodiments, the source of an element A is at least one selected from the elementary substance, oxide, phosphate, oxalate, carbonate and sulfate of the element A, the source of an element B is at least one selected from the elementary substance, oxide, phosphate, oxalate, carbonate and sulfate of the element B, the source of an element C is at least one selected from the sulfate, borate, nitrate and silicate of the element C, and the source of an element D is at least one selected from the elementary substance and an ammonium salt of the element D.
In some embodiments, the grinding and mixing of step (2) are carried out for 8 to 15 h.
In some embodiments, the sintering of step (4) is carried out in a temperature range of 600° C. to 900° C. for 6 to 14 h.
In some embodiments, the present application provides a secondary battery, comprising the positive electrode plate according to any one of the above embodiments.
In some embodiments, the present application provides a power consuming device comprising the above secondary battery.
The positive electrode plate generally includes a positive electrode current collector and a positive electrode film layer provided on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is provided on either or both of opposite surfaces of the positive electrode current collector.
In some embodiments, the positive current collector can be a metal foil or a composite current collector. For example, as a metal foil, an aluminum foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (aluminum, an aluminum alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode film layer may optionally comprise a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluorine-containing acrylate resin.
In some embodiments, the positive electrode film layer also optionally comprises 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 plate can be prepared as follows: dispersing the above-mentioned components for preparing the positive electrode plate, such as a positive electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., N-methyl pyrrolidone) to form a positive electrode slurry; and coating the positive electrode current collector with the positive electrode slurry, followed by the procedures such as drying and cold pressing, so as to obtain the positive electrode plate.
[Negative Electrode Plate]
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer provided on at least one surface of the negative electrode current collector, the negative electrode film layer comprising a negative electrode active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is provided on either or both of the two opposite surfaces of the negative electrode current collector.
In some embodiments, the negative current collector may be a metal foil or a composite current collector. For example, as a metal foil, a copper foil can be used. The composite current collector may comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by forming a metal material (copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver and a silver alloy, etc.) on a polymer material substrate (e.g., polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative electrode active material can be a negative electrode active material known in the art for batteries. As an example, the negative electrode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, a silicon-based material, a tin-based material and lithium titanate, etc. The silicon-based material may be at least one selected from elemental silicon, silicon oxides, silicon carbon composites, silicon nitrogen composites and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxides, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as negative electrode active materials for batteries can also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer may optionally comprise a binder. As an example, the binder may be at least one selected from a 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 may optionally comprise a conductive agent. As an example, the conductive agent may be at least one selected from superconductive carbon, acetylene black, carbon black, ketjenblack, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally comprise other auxiliary agents, such as thickener (e.g. sodium carboxymethyl cellulose (CMC-Na)) and the like.
In some embodiments, the negative electrode plate can be prepared as follows: dispersing the above-mentioned components for preparing the negative electrode plate, such as negative electrode active material, conductive agent, binder and any other components, in a solvent (e.g. deionized water) to form a negative electrode slurry; and coating a negative electrode current collector with the negative electrode slurry, followed by procedures such as drying and cold pressing, so as to obtain the negative electrode plate.
[Electrolyte]
The electrolyte functions to conduct ions between the positive electrode plate and the negative electrode plate. The type of the electrolyte is not specifically limited in the present application, and can be selected according to actual requirements. For example, the electrolyte may be in a liquid state, a gel state or an all-solid state.
In some embodiments, the electrolyte is liquid and includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be at least one selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalate borate, lithium dioxalate borate, lithium difluorodioxalate phosphate and lithium tetrafluorooxalate phosphate.
In some embodiments, the solvent may be at least one selected from ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl 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, ethyl methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally comprises an additive. As an example, the additive may include a negative electrode film-forming additive and a positive electrode film-forming additive, and may further include an additive that can improve some performance of the battery, such as an additive that improves overcharge performance of the battery, or an additive that improves high-temperature performance or low-temperature performance of the battery.
[Separator]
In some embodiments, the secondary battery further comprises a separator. The type of the separator is not particularly limited in the present application, and any well known porous-structure separator with good chemical stability and mechanical stability may be selected.
In some embodiments, the material of the separator may be at least one selected from glass fibers, non-woven fabrics, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be either a single-layer film or a multi-layer composite film, and is not limited particularly. When the separator is a multi-layer composite film, the materials in the respective layers may be same or different, which is not limited particularly.
In some embodiments, an electrode assembly may be formed by a positive electrode plate, a negative electrode plate and a separator by a winding process or a stacking process.
In some embodiments, the secondary battery may comprise an outer package. The outer package can be used to encapsulate the above-mentioned electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery can be a hard shell, for example, a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the secondary battery may also be a soft bag, such as a pouch-type soft bag. The material of the soft bag may be plastics, and the examples of plastics may include polypropylene, polybutylene terephthalate, polybutylene succinate, etc.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square or of any other shape. For example,
In some embodiments, with reference to
In some embodiments, the secondary battery can be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
Optionally, the battery module 4 may also comprise a housing with an accommodating space, and a plurality of secondary batteries 5 are accommodated in the accommodating space.
In some embodiments, the above battery module may also be assembled into a battery pack, the number of the battery modules contained in the battery pack may be one or more, and the specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
In addition, the present application further provides a power consuming device. The power consuming device comprises at least one of the secondary battery, battery module, or battery pack provided by the present application. The secondary battery, battery module or battery pack can be used as a power source of the power consuming device or as an energy storage unit of the power consuming device. The power consuming device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, ship, and satellite, an energy storage system, etc., but is not limited thereto.
As for the power consuming device, the secondary battery, battery module or battery pack can be selected according to the usage requirements thereof.
Specific Examples of New Positive Electrode Active Material
Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The examples in which techniques or conditions are not specified are based on the techniques or conditions described in documents in the art or according to the product introduction. The reagents or instruments used therein for which manufacturers are not specified are all conventional products that are commercially available.
I. Preparation of Secondary Battery
1) Preparation of a Positive Electrode Active Material
Preparation of doped manganese oxalate: 1.3 mol of MnSO4·H2O and 0.7 mol of FeSO4·H2O are mixed thoroughly for 6 hours in a mixer. The mixture is transferred into a reaction kettle, and 10 L of deionized water and 2 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain an Fe-doped manganese oxalate suspension. Then, the suspension is filtered, and the resultant filter cake is dried at 120° C. and then ground, so as to obtain Fe-doped manganese oxalate particles with a median particle size Dv50 of about 100 nm.
Preparation of doped lithium manganese phosphate: 1 mol of the above manganese oxalate particles, 0.497 mol of lithium carbonate, 0.001 mol of Mo(SO4)3, an 85% aqueous phosphoric acid solution containing 0.999 mol of phosphoric acid, 0.001 mol of H4SiO4, 0.0005 mol of NH4HF2, and 0.005 mol of sucrose are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon-coated Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001. The positive electrode active material may be tested for element content using inductively coupled plasma (ICP) emission spectroscopy.
2) Preparation of Button Battery
The above positive electrode active material, polyvinylidene fluoride (PVDF) and acetylene black in a weight ratio of 90:5:5 are added into N-methylpyrrolidone (NMP), and stirred in a drying room to make a slurry. An aluminum foil is coated with the above slurry, followed by drying and cold pressing, so as to obtain a positive electrode plate. The positive electrode film layer has a single-side surface density of 0.02 g/cm2 and a compacted density of 2.0 g/cm3.
A lithium plate is used as a negative electrode, a solution of 1 mol/L LiPF6 in ethylene carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (DMC) in a volume ratio of 1:1:1 is used as an electrolyte, and the lithium plate and the electrolyte are assembled, together with the positive electrode plate prepared above, into a button battery in a button battery box.
3) Preparation of Full Battery
The above positive electrode active material is uniformly mixed with a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in a weight ratio of 92:2.5:5.5 in an N-methylpyrrolidone solvent system, and the mixture is applied to an aluminum foil, followed by drying and cold pressing, so as to form a positive electrode film layer, to obtain a positive electrode plate. The positive electrode film layer has a single-side surface density of 0.04 g/cm2 and a compacted density of 2.4 g/cm3.
Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are uniformly mixed in deionized water in a weight ratio of 90:5:2:2:1, and the mixture is applied to a copper foil, followed by drying and cold pressing, so as to form a negative electrode film layer, to obtain a negative electrode plate. The negative electrode film layer has a single-side surface density of 0.02 g/cm2 and a compacted density of 1.7 g/cm3.
With a polyethylene (PE) porous polymer film as a separator, the positive electrode plate, the separator and the negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode and the negative electrode to play a role of isolation, and then winding is performed to obtain a bare cell. The bare cell is placed in an outer package, and the same electrolyte as that for the preparation of the button battery is injected, followed by encapsulation, so as to obtain a full battery.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.4885 mol, Mo(SO4)3 is replaced by MgSO4, the amount of FeSO4·H2O is changed into 0.68 mol, 0.02 mol of Ti(SO4)2 is also added in the preparation of doped manganese oxalate, and H4SiO4 is replaced by HNO3, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.496 mol, Mo(SO4)3 is replaced by W(SO4)3, and H4SiO4 is replaced by H2SO4, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of high-purity Li2CO3 is changed into 0.4985 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Al2(SO4)3, and NH4HF2 is replaced by NH4HCl2, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, 0.7 mol of FeSO4·H2O is changed into 0.69 mol, 0.01 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4965 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, and H4SiO4 is replaced by H2SO4, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.68 mol, 0.01 mol of VCl2 and 0.01 mol of MgSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4965 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, and H4SiO4 is replaced by H2SO4, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, MgSO4 is replaced by CoSO4, the rest are the same as in example 6.
Except that in “1) Preparation of positive electrode active material”, MgSO4 is replaced by NiSO4, the rest are the same as in example 6.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.698 mol, 0.002 mol of Ti(SO4)2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4955 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, H4SiO4 is replaced by H2SO4, and NH4HF2 is replaced by NH4HCl2, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.68 mol, 0.01 mol of VCl2 and 0.01 mol of MgSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4975 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.0005 mol of Nb2(SO4)5, and NH4HF2 is replaced by NH4HBr2, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.69 mol, 0.01 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.499 mol, Mo(SO4)3 is replaced by MgSO4, and NH4HF2 is replaced by NH4HBr2, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.36 mol, the amount of FeSO4·H2O is changed into 0.6 mol, 0.04 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4985 mol, Mo(SO4)3 is replaced by MgSO4, and H4SiO4 is replaced by HNO3, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.16 mol, and the amount of FeSO4·H2O is changed into 0.8 mol, the rest are the same as in example 12.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.3 mol, and the amount of VCl2 is changed into 0.1 mol, the rest are the same as in example 12.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.494 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, and H4SiO4 is replaced by H2SO4, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.467 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, 0.001 mol of H4SiO4 is replaced by 0.005 mol of H2SO4, and 1.175 mol of 85% phosphoric acid is replaced by 1.171 mol of 85% phosphoric acid, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, 0.1 mol of VCl2 is also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.492 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, H4SiO4 is replaced by H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.5 mol, 0.1 mol of VCl2 and 0.1 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.492 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, H4SiO4 is replaced by H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of FeSO4·H2O is changed into 0.4 mol, and 0.1 mol of CoSO4 is changed into 0.2 mol, the rest are the same as in example 18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.5 mol, and the amount of FeSO4·H2O is changed into 0.1 mol, and the amount of CoSO4 is changed into 0.3 mol, the rest are the same as in example 18.
Except that in “1) Preparation of positive electrode active material”, 0.1 mol of CoSO4 is replaced by 0.1 mol of NiSO4, the rest are the same as in example 18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.5 mol, and the amount of FeSO4·H2O is changed into 0.2 mol, and 0.1 mol of CoSO4 is replaced by 0.2 mol of NiSO4, the rest are the same as in example 18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, and the amount of FeSO4·H2O is changed into 0.3 mol, and the amount of CoSO4 is changed into 0.2 mol, the rest are the same as in example 18.
Except that in “1) Preparation of positive electrode active material”, 1.3 mol of MnSO4·H2O is changed into 1.2 mol, 0.7 mol of FeSO4·H2O is changed into 0.5 mol, 0.1 mol of VCl2 and 0.2 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.497 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, H4SiO4 is replaced by H2SO4, and 0.0005 mol of NH4HF2 is changed into 0.0025 mol, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.0 mol, and the amount of FeSO4·H2O is changed into 0.7 mol, and the amount of CoSO4 is changed into 0.2 mol, the rest are the same as in example 18.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.3 mol, 0.1 mol of VCl2 and 0.2 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.4825 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, the amount of H4SiO4 is changed into 0.1 mol, the amount of phosphoric acid is changed into 0.9 mol, and the amount of NH4HF2 is changed into 0.04 mol, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.3 mol, 0.1 mol of VCl2 and 0.2 mol of CoSO4 are also added in the preparation of doped manganese oxalate, the amount of Li2CO3 is changed into 0.485 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, the amount of H4SiO4 is changed into 0.08 mol, the amount of phosphoric acid is changed into 0.92 mol, and the amount of NH4HF2 is changed into 0.05 mol, the rest are the same as in example 1.
Preparation of manganese oxalate: 1 mol of MnSO4·H2O is added into a reaction kettle, and 10 L of deionized water and 1 mol of oxalic acid dihydrate (in oxalic acid) are added. The reaction kettle is heated to 80° C., stirring is performed for 6 hours at a rotation speed of 600 rpm, and the reaction is completed (no bubbles are generated), so as to obtain a manganese oxalate suspension. Then, the suspension is filtered, and the resultant filter cake is dried at 120° C. and then ground, to obtain manganese oxalate particles with a median particle size Dv50 of about 50 to 200 nm.
Preparation of lithium manganese phosphate: 1 mol of the above manganese oxalate particles, 0.5 mol of lithium carbonate, an 85% aqueous phosphoric acid solution containing 1 mol of phosphoric acid and 0.005 mol of sucrose are added into 20 L of deionized water. The mixture is transferred into a sander and thoroughly ground and stirred for 10 hours to obtain a slurry. The slurry is transferred into a spray drying apparatus for spray-drying granulation, where the drying temperature is set at 250° C. and the drying time is 4 h, so as to obtain particles. The above powder is sintered at 700° C. for 10 hours in a protective atmosphere of nitrogen (90% by volume)+hydrogen (10% by volume), so as to obtain carbon-coated LiMnPO4.
Except that in comparative example 1, 1 mol of MnSO4·H2O is replaced by 0.85 mol of MnSO4·H2O and 0.15 mol of FeSO4·H2O, which are added into a mixer and thoroughly mixed for 6 h before adding into a reaction kettle, the rest are the same as in comparative example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.9 mol, 0.7 mol of FeSO4·H2O is replaced by 0.1 mol of ZnSO4, the amount of Li2CO3 is changed into 0.495 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of MgSO4, the amount of phosphoric acid is changed into 1 mol, and no H4SiO4 and NH4HF2 is added, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, the amount of FeSO4·H2O is changed into 0.8 mol, the amount of Li2CO3 is changed into 0.45 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.005 mol of Nb2(SO4)5, 0.999 mol of phosphoric acid is changed into 1 mol, 0.0005 mol of NH4HF2 is changed into 0.025 mol, and no H4SiO4 is added, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.6 mol, the amount of Li2CO3 is changed into 0.38 mol, and 0.001 mol of Mo(SO4)3 is replaced by 0.12 mol of MgSO4, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 0.8 mol, 0.7 mol of FeSO4·H2O is replaced by 1.2 mol of ZnSO4, the amount of Li2CO3 is changed into 0.499 mol, and 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.4 mol, the amount of FeSO4·H2O is changed into 0.6 mol, the amount of Li2CO3 is changed into 0.534 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the amount of phosphoric acid is changed into 0.88 mol, the amount of H4SiO4 is changed into 0.12 mol, and the amount of NH4HF2 is changed into 0.025 mol, the rest are the same as in example 1.
Except that in “1) Preparation of positive electrode active material”, the amount of MnSO4·H2O is changed into 1.2 mol, the amount of FeSO4·H2O is changed into 0.8 mol, the amount of Li2CO3 is changed into 0.474 mol, 0.001 mol of Mo(SO4)3 is replaced by 0.001 mol of MgSO4, the amount of phosphoric acid is changed into 0.93 mol, the amount of H4SiO4 is changed into 0.07 mol, and the amount of NH4HF2 is changed into 0.06 mol, the rest are the same as in example 1.
II. Method for Testing Properties of Positive Electrode Active Material and Battery Performance
1. Method for Measuring Lattice Change Rate
In a constant-temperature environment at 25° C., a positive electrode active material sample is placed in XRD (model: Bruker D8 Discover) and tested at 1°/min, and the test data are sorted and analyzed; and with reference to the standard PDF card, the lattice constants a0, b0, c0, and v0 at this time are calculated (a0, b0, and c0 represent the lengths of a unit cell on all sides, and v0 represents the volume of the unit cell, which could be obtained directly from XRD refinement results).
By using the method for preparing a button battery in the above-mentioned examples, the positive electrode active material sample is made into a button battery, and the button battery is charged at a small rate of 0.05C until the current is reduced to 0.01 C. Then a positive electrode plate in the button battery is taken out and soaked in DMC for 8 h. Then the positive electrode plate is dried, powder is scraped off, and particles with a particle size of less than 500 nm are screened out. Sampling is performed, and a lattice constant v1 is calculated in the same way as that for testing the fresh sample as described above. (v0−v1)/v0×100% is shown in a table as a lattice change rate of the sample before and after complete lithium intercalation and de-intercalation.
2. Method for Measuring Li/Mn Antisite Defect Concentration
The XRD results determined in the “Method for measuring lattice change rate” are compared with the PDF (Powder Diffraction File) card of a standard crystal, so as to obtain a Li/Mn antisite defect concentration. Specifically, the XRD results determined in the “Method for measuring lattice change rate” are imported into a general structure analysis system (GSAS) software, and refinement results are obtained automatically, including the occupancies of different atoms; and a Li/Mn antisite defect concentration is obtained by reading the refinement results.
3. Method for Measuring Surface Oxygen Valence State
5 g of a positive electrode active material is made into a button battery according to the method for preparing a button battery in the above-mentioned examples. The button battery is charged at a small rate of 0.05 C until the current is reduced to 0.01 C. Then a positive electrode plate in the button battery is taken out and soaked in DMC for 8 h. Then the positive electrode plate is dried, powder is scraped off, and particles with a particle size of less than 500 nm are screened out. The obtained particles are measured with electron energy loss spectroscopy (EELS, instrument model used: Talos F200S), so as to obtain an energy loss near-edge structure (ELNES) which reflects the density of states and energy level distribution of an element. According to the density of states and energy level distribution, the number of occupied electrons is calculated by integrating the data of valence-band density of states, and then a valence state of surface oxygen after the charging is extrapolated.
4. Method for Measuring Compacted Density
5 g of powder is put into a compaction dedicated mold (U.S. CARVER mold, model: 13 mm), and then the mold is placed on a compacted density instrument. A pressure of 3T is exerted, the thickness (after pressure relief) of the powder under pressure is read from the instrument, and a compacted density is calculated through p=m/v.
5. Method for Measuring Dissolution of Mn (and Fe Doping Mn-Site) after Cycling
A full battery after cycling to 80% attenuated capacity at 45° C. is discharged to a cut-off voltage of 2.0 V at a rate of 0.1 C. The battery is then disassembled, a negative electrode plate is taken out, a round piece of 30 unit areas (1540.25 mm2) is randomly taken from the negative electrode plate, and inductively coupled plasma (ICP) emission spectroscopy is performed using Agilent ICP-OES730. The amounts of Fe (if the Mn-site of the positive electrode active material is doped with Fe) and Mn therein are calculated according to the ICP results, and then the dissolution of Mn (and Fe doping the Mn-site) after cycling is calculated. The testing standard is in accordance with EPA-6010D-2014.
6. Method for Measuring Initial Gram Capacity of Button-Type Battery
At 2.5 to 4.3 V, a button battery is charged at 0.1 C to 4.3 V, then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA, allowed to stand for 5 min, and then discharged at 0.1 C to 2.0 V; and the discharge capacity at this moment is the initial gram capacity, marked as DO.
7. Method for Measuring 3 C Charge Constant Current Rate
In a constant-temperature environment at 25° C., a fresh full battery is allowed to stand for 5 min, and discharged at ⅓C to 2.5 V. The full battery is allowed to stand for 5 min, charged at ⅓C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is left to stand for 5 min, and the charge capacity at this time is recorded as CO. The full battery is discharged at ⅓C to 2.5 V, allowed to stand for 5 min, then charged at 3 C to 4.3 V, and allowed to stand for 5 min, and the charge capacity at this moment is recorded as C1. The charge constant current rate at 3 C is C1/CO×100%.
A higher 3 C charge constant current rate indicates a better rate performance of the battery.
8. Test of Cycle Performance of Full Battery at 45° C.
In a constant-temperature environment at 45° C., at 2.5 to 4.3 V, a full battery is charged at 1 C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and then discharged at 1 C to 2.5 V, and the discharge capacity at this moment is recorded as DO. The above-mentioned charge/discharge cycle is repeated until the discharge capacity is reduced to 80% of DO. The number of cycles experienced by the battery at this time is recorded.
9. Test of Expansion of Full Battery at 60° C.
At 60° C., a full battery with 100% SOC (State of Charge) is stored. Before and after and during the storage, the open-circuit voltage (OCV) and AC internal impedance (IMP) of a cell are measured for monitoring the SOC, and the volume of the cell is measured. Herein, the full battery is taken out after every 48 h of storage, and allowed to stand for 1 h, then the OCV and internal IMP are measured, and the cell volume is measured with the displacement method after the full battery is cooled to room temperature. The water displacement method means that the gravity F1 of the battery cell is measured separately using a balance with automatic unit conversion of on-board data, the battery cell is then completely placed in deionized water (with a density known to be 1 g/cm3), the gravity F2 of the battery cell at this time is measured, the buoyancy Fbuoyancy on the battery cell is F1−F2, and the battery cell volume is calculated as V=(F1−F2)/(ρ×g) according to the Archimedes' principle Fbuoyancy=ρ×g×Vdisplacement.
From the test results of OCV and IMP, the battery of the example always maintains a SOC of no less than 99% in the experimental process till the end of the storage.
After 30 days of storage, the cell volume is measured, and a percentage increase in cell volume after the storage relative to the cell volume before the storage is calculated.
In addition, residual capacity of the cell is measured. At 2.5 to 4.3 V, the full battery is charged at 1 C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and the charge capacity at this moment is recorded as the residual capacity of the cell.
Table 1 shows the compositions of the positive electrode active materials of Examples 1 to 11 and Comparative examples 1 to 8. Table 2 shows the performance data of the positive electrode active materials or button batteries or full batteries of Examples 1 to 11 and Comparative examples 1 to 8 obtained according to the above-mentioned performance testing methods. Table 3 shows the compositions of the positive electrode active materials of Examples 12 to 27. Table 4 shows the performance data of the positive electrode active materials or button batteries or full batteries of Examples 12 to 27 obtained according to the above-mentioned performance testing methods.
A positive electrode active material, a button battery and a full battery are prepared in the same way as in example 1, except that the stirring speed and temperature in the preparation of doped manganese oxalate, the time of grinding and stirring in a sander, and the sintering temperature and sintering time are changed, specifically as shown in Table 5 below.
Also, the performance data of the positive electrode active materials or button batteries or full batteries of Examples 28 to 41 obtained according to the above-mentioned performance testing methods are shown in Table 6.
A positive electrode active material, a button battery and a full battery are prepared in the same way as in example 1, except that the lithium source, the manganese source, the phosphorus source and the sources of doping elements A, B, C and D are changed, specifically as shown in Table 7 below. The prepared positive electrode active materials all had the same composition as in Example 1, namely, Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001.
Also, the performance data of the positive electrode active materials or button batteries or full batteries of examples 42 to 54 obtained according to the above-mentioned performance testing methods are shown in Table 8.
It can be seen from Tables 2, 4, 6 and 8 above that, the positive electrode active materials of the examples of the present application all achieve a better effect than the comparative examples in one or even all terms of cycle performance, high-temperature stability, gram capacity and compacted density.
Through comparison between Examples 18 to 20 and 23 to 25, it can be seen that in the case of the same rest elements, when (1-y):y is in a range of 1 to 4, the energy density and cycle performance of the secondary battery can be further improved.
Specific Examples about the New Conductive Undercoat Layer
Hereinafter, the examples of the present application will be explained. The examples described below are exemplary and are merely for explaining the present application, and should not be construed as limiting the present application. The examples in which techniques or conditions are not specified are based on the techniques or conditions described in documents in the art or according to the product introduction. The reagents or instruments used therein for which manufacturers are not specified are all conventional products that are commercially available.
For the distinguishment from the new positive electrode material in the above specific examples, the specific examples of the new conductive undercoat layer are marked with a suffix P after the number.
1. Provision of First Polymer
In the following examples, the first polymer is a hydrogenated carboxylated nitrile rubber, which contains a first monomeric unit, a second monomeric unit, a third monomeric unit, and a fourth monomeric unit. The weight percentages of the first monomeric unit, the second monomeric unit, the third monomeric unit, and the fourth monomeric unit in the polymer and the weight-average molecular weight of the first polymer are as shown in Table 1P.
The first monomeric unit is a monomeric unit represented by formula 1;
the second monomeric unit is at least one selected from a group consisting of a monomeric unit represented by formula 2 and a monomeric unit represented by formula 3
the third monomeric unit is at least one selected from a group consisting of a monomeric unit represented by formula 4 and a monomeric unit represented by formula 5
the fourth monomeric unit is a monomeric unit represented by formula 6:
In this example, R1, R2, and R3 are all H, and R4 is n-butyl.
2. Preparation of Aluminum Foil with Conductive Undercoat Layer
The first polymer, the first water-based binder (a polyacrylic acid-acrylate copolymer, a weight-average molecular weight of 340,000) and the first conductive agent (SP) are dissolved/dispersed at a weight ratio of 15:40:45 into deionized water and formulated as a conductive undercoat layer slurry.
The conductive undercoat layer slurry is applied to both sides of an aluminum foil, and after drying, a conductive undercoat layer with a thickness of 5 m is formed on each side. An aluminum foil with a conductive undercoat layer is obtained.
3) Preparation of Positive Electrode Plate
The positive electrode active material (Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001) prepared in the above example 1, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) are mixed uniformly in an N-methylpyrrolidone solvent system at a weight ratio of 92:2.5:5.5, to obtain the positive electrode slurry, the positive electrode slurry is coated on both sides of the aluminum foil with a conductive undercoat layer, followed by drying and cold pressing, to form a positive electrode film layer, so as to obtain a positive electrode plate. The positive electrode film layer has a single-side surface density of 0.025 g/cm2 and a compacted density of 2.4 g/cm3.
4) Preparation of Negative Electrode Plate
Negative electrode active materials artificial graphite and hard carbon, a conductive agent acetylene black, a binder styrene butadiene rubber (SBR) and a thickening agent sodium carboxymethylcellulose (CMC) are uniformly mixed in deionized water in a weight ratio of 90:5:2:2:1, and the mixture is applied to a copper foil, followed by drying and cold pressing, so as to form a negative electrode film layer, to obtain a negative electrode plate. The negative electrode film layer has a surface density of 0.013 g/cm2 on one side and a compacted density of 1.7 g/cm3.
5) Packaging of Full Battery
With a polyethylene (PE) porous polymer film as a separator, the positive electrode plate, the separator and the negative electrode plate are stacked in sequence, such that the separator is located between the positive electrode and the negative electrode to play a role of isolation, and then winding is performed to obtain a bare cell. The bare battery cell is placed in an outer package, which is injected with the above electrolyte and packaged to obtain the full battery.
The weight of the positive electrode active substance in a single full battery is 565.66 g; and the weight of the negative electrode active substance is 309.38 g.
Examples 2P-27P are different from example 1 by step 3). Other step parameters are the same as those in example 1P.
The positive electrode active materials used in step 3) in examples 2P-27P are the positive electrode active materials in the above examples 2-27 respectively.
Examples 1P-9P are different from example 1P by steps 2) and 3). Other step parameters are the same as those in example 1P.
In comparative examples 1P-9P, in steps 2) and 3), no aluminum foil with a conductive undercoat layer is prepared, and the positive electrode slurry is directly coated onto the aluminum foil, followed by drying, and cold pressing to form the positive electrode film layer, so as to obtain the positive electrode plate.
The positive electrode active materials used in step 3) of comparative examples 1P-8P are the positive electrode active materials of the above comparative examples 1-8, respectively.
The positive electrode active material used in step 3) of comparative example 9P is the positive electrode active material of the above example 1.
Comparative example 10P is different from example 1P by step 2). Other step parameters are the same as those in example 1P.
In step 2) of comparative example 10P, the first water-based binder (a polyacrylic acid-acrylate copolymer) and the first conductive agent (SP), at a weight ratio of 40:45, are dissolved/dispersed in deionized water, and formulated as a conductive undercoat layer slurry. The conductive undercoat layer slurry is coated onto an aluminum foil, and dried to form a conductive undercoat layer with a thickness of 5 m. An aluminum foil with a conductive undercoat layer is obtained.
Comparative example 11P is different from example 1P by step 2). Other step parameters are the same as those in example 1P.
In step 2) of comparative example 11P, the polymer I, the first water-based binder (a polyacrylic acid-acrylate copolymer) and the first conductive agent (SP), at a weight ratio of 15:40:45, are dissolved/dispersed in deionized water, and formulated as a conductive undercoat layer slurry. The conductive undercoat layer slurry is coated onto an aluminum foil, and dried to form a conductive undercoat layer with a thickness of 5 m. An aluminum foil with a conductive undercoat layer is obtained.
The difference between the polymer I and the first polymer is that the compositions of the polymer are different, and the composition of the polymer I and the weight-average molecular weight of the polymer I are shown in Table 2P below.
Comparative example 12P is different from example 1P by step 2). Other step parameters are the same as those in example 1P.
In step 2) of comparative example 12P, the first polymer, the I binder (polyacrylic acid, a weight-average molecular weight of 350,000) and the first conductive agent (SP), at a weight ratio of 15:40:45, are dissolved/dispersed in deionized water, and formulated as a conductive undercoat layer slurry. The conductive undercoat layer slurry is applied to an aluminum foil, and after drying, a conductive undercoat layer with a thickness of 5 m is formed. An aluminum foil with a conductive undercoat layer is obtained.
Analysis and Tests
1. Test of Adhesive Force of Positive Electrode Plate
2. Test of DC Resistance Value of Battery
At 25° C., the battery is charged to 4.3 V at a constant current and constant voltage at 1.0 C (1.0 C referred to the nominal capacity); and at a rate of 1.0 C, the power of the battery is adjusted to 50% SOC. After standing for 5 min, the battery is discharged at 4 C at a constant current (Im) for 30 s (voltage data are collected once every 1 s), the initial voltage U0 and the voltage U30 after 30 s of discharge are recorded, and the value of DC resistance (DCR) is calculated according to the following equation.
Value of DC resistance=(U0−U30)/Im
Taking the direct current resistance value of the battery of example 1P as 100%, the changes of other examples and comparative examples relative to example 1P are expressed in percentage form.
3. Number of Cycles of the Battery at a Capacity Retention Rate of 80% at 45° C. (Hereinafter Referred to as “Number of Cycles for 80% Capacity”)
In a constant-temperature environment at 45° C., at 2.5 to 4.3 V, a full battery is charged at 1 C to 4.3 V, and then charged at a constant voltage of 4.3 V until the current is less than or equal to 0.05 mA. The full battery is allowed to stand for 5 min, and then discharged at 1 C to 2.5 V, and the discharge capacity at this moment is recorded as D0. The above-mentioned charge/discharge cycle is repeated until the discharge capacity is reduced to 80% of D0. The number of cycles experienced by the battery at this time is recorded.
According to the above-mentioned detection and analysis methods, the adhesive force, the direct-current resistance value of the battery and the number of cycles for capacity retention rate of 80% at 45° C. of the positive electrode plates prepared in the above examples 1P-27P and comparative examples 9P-12P are tested, and the results are shown in Table 3P below.
It can be seen from Table 3P that the positive electrode plates of examples 1P-27P show improved adhesive forces, and the batteries of examples 1P-27P show reduced direct-current resistance and increased cycle capacity retention rate.
Comparative example 9P (without a conductive undercoat layer), comparative example 10P (without a first polymer), comparative example 11P (replacing the first polymer with a polymer I), comparative example 12P (replacing the first water-based binder with an I binder) fail to achieve the effect of the above-mentioned improvement.
Examples 28P-34P are different from example 1P by step 2). Other step parameters are the same as those in example 1P.
In step 2), the compositions of the first polymer used in examples 28P-34P are different from those in example 1P, and specifically the weight percentages of the second monomeric unit and the third monomeric unit are different from those in example 1P. The compositions of the first polymers in examples 28P-34P are shown in Table 4P below.
Examples 35P-39P are different from example 1P by step 2). Other step parameters are the same as those in example 1P.
In step 2), the thickness of the conductive undercoat layer in examples 28P-34P is different from that in Example 1P, see Table 5P for details.
Examples 40P-45P are different from example 1P by step 2). Other step parameters are the same as those in example 1P.
In step 2), the composition of the conductive undercoat layer (the ratio of the first polymer, the first water-based binder to the first conductive agent) of examples 40P-45P is different from that in example 1, see Table 6P for details.
According to the above-mentioned testing and analysis methods, the adhesive force, the direct-current resistance value of the battery and the number of cycles for capacity retention rate of 80% at 45° C. of the positive electrode plates prepared in the above examples 1P, and 28P-45P are tested, and the results are shown in Table 7P below.
It can be seen from Table 7P that the positive electrode plates of examples 28P-45P show improved adhesive forces, and the batteries of examples 28P-45P show reduced direct-current resistance and increased cycle capacity retention rate. When the value of M3/(M2+M3) is 0-5%, the battery exhibited a significant decrease in direct current impedance.
Examples 46P-54P are different from example 1P by step 3). Other step parameters are the same as those in example 1P.
In step 3) in examples 46P-54P, the positive electrode active material (Li0.994Mo0.001Mn0.65Fe0.35P0.999Si0.001O3.999F0.001) prepared in the above example 1, and a conductive agent acetylene black, a binder polyvinylidene fluoride (PVDF), a dispersant and an infiltration agent are mixed uniformly in an N-methylpyrrolidone solvent system at a weight ratio of (92−Y1−Y2):2.5:5.5:Y1:Y2, to obtain a positive electrode slurry, the positive electrode slurry is coated on both sides of the aluminum foil with a conductive undercoat layer, followed by drying and cold pressing, to form a positive electrode film layer, so as to obtain a positive electrode plate. The positive electrode film layer has a single-side surface density of 0.025 g/cm2 and a compacted density of 2.4 g/cm3.
The infiltration agent in examples 46P-54P is a maleic anhydride-styrene copolymer (molecular weight: 5000). The dispersant of examples 46P-54P is the second polymer.
In the positive electrode plates of examples 46P-54P, the first polymer (from the conductive undercoat layer) and the second polymer (from the positive electrode film layer) are different.
The second polymer is a hydrogenated nitrile rubber, which contains a fifth monomeric unit, a sixth monomeric unit, and a seventh monomeric unit. The weight percentages of the five monomeric unit, the sixth monomeric unit and the seventh monomeric unit in the polymer, and the weight-average molecular weight of the second polymer are shown in Table 8P.
The fifth monomeric unit is a monomeric unit represented by formula 7;
the sixth monomeric unit is at least one selected from a group consisting of a monomeric unit represented by formula 8 and a monomeric unit represented by formula 9
the seventh monomeric unit is at least one selected from a group consisting of a monomeric unit represented by formula 10 and a monomeric unit represented by formula 11
In step 3) in examples 46P-54P, the proportions of the dispersant (second polymer) Y and the proportions of the infiltration agent (a maleic anhydride-styrene copolymer) Y2 and the ratio thereof Y1/Y2 are shown in Table 9P below.
In the positive electrode plates of examples 46P-54P, the mass ratio of the first polymer (from the conductive undercoat layer) to the second polymer (from the positive electrode film layer) is 2:1.
According to the above-mentioned testing and analysis methods, the adhesive force, the direct-current resistance value of the battery and the number of cycles for capacity retention rate of 80% at 45° C. of the positive electrode plates prepared in the above examples 1P, and 46P-54P are tested, and the results are shown in Table 10P below.
As shown in Table 10P, on the basis of the above new conductive undercoat layer, combined with a new positive electrode film layer containing a dispersant and an infiltration agent, the adhesive force of the electrode plate can be further improved, and/or the direct-current resistance of the battery can be reduced, and/or the cycling performance of the battery is improved.
As could be seen from the above experimental data, the present application provides a new positive electrode plate, a secondary battery, and a power consuming device. The positive electrode plate comprises a new positive electrode active material and a new conductive undercoat layer.
The new positive electrode active materials achieve better effects in one or even all aspects of cycling performance, high-temperature stability, gram capacity and compacted density.
The new conductive undercoat layer achieves better effects in one or even all aspects of providing the adhesive force of the electrode plate, reducing the direct-current resistance of the battery, and improving the cycling performance of the battery.
It should be noted that the present application is not limited to the above embodiments. The above embodiments are exemplary only, and any embodiment that has substantially same constitutions as the technical ideas and has the same effects within the scope of the technical solution of the present application falls within the technical scope of the present application. In addition, without departing from the gist of the present application, various modifications that can be conceived by those skilled in the art to the embodiments, and other modes constructed by combining some of the constituent elements of the embodiments also fall within the scope of the present application.
This application is a continuation of International Application No. PCT/CN2022/084556, filed on Mar. 31, 2022, the entire content of which is incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/084556 | Mar 2022 | US |
| Child | 18354610 | US |
