CN118507662A - Positive electrode active material, positive electrode sheet, battery, and electricity using device - Google Patents
Positive electrode active material, positive electrode sheet, battery, and electricity using device Download PDFInfo
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- CN118507662A CN118507662A CN202310126504.7A CN202310126504A CN118507662A CN 118507662 A CN118507662 A CN 118507662A CN 202310126504 A CN202310126504 A CN 202310126504A CN 118507662 A CN118507662 A CN 118507662A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 81
- 230000005611 electricity Effects 0.000 title description 2
- 239000011149 active material Substances 0.000 claims abstract description 83
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 65
- 239000011572 manganese Substances 0.000 claims abstract description 39
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 31
- 239000010452 phosphate Substances 0.000 claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims description 15
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 229910013100 LiNix Inorganic materials 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 description 15
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- 238000007599 discharging Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
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- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses a positive electrode active material, a positive electrode plate, a battery and an electric device, wherein the positive electrode active material comprises the following components: a first active material comprising a lithium-rich manganese-based material, the first active material having a gram capacity of not less than 150mAh/g in the range of 2.5V-4.35V; a second active material comprising a lithium-containing phosphate. Thus, a positive electrode active material having a higher energy density and a better cycle life can be obtained.
Description
Technical Field
The application relates to the field of energy, in particular to a positive electrode active material, a positive electrode plate, a battery and an electric device.
Background
In recent years, with the development of lithium ion battery technology, lithium ion batteries are widely applied to energy storage power supply systems of hydraulic power, firepower, wind power, solar power stations and the like, and have wide application in a plurality of fields of electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment, aerospace and the like. At present, the lithium ion battery still has more problems to be solved in the aspect of industrial production and application.
Disclosure of Invention
In one aspect of the present application, the present application provides a positive electrode active material comprising: a first active material comprising a lithium-rich manganese-based material, the first active material having a gram capacity of not less than 150mAh/g in the range of 2.5V-4.35V; a second active material comprising a lithium-containing phosphate. Thus, a positive electrode active material having a higher energy density and a better cycle life can be obtained.
According to an embodiment of the present application, the chemical formula of the first active material satisfies nLi 2MnO3·(1-n)LiNixMn(1-x-y)MyO2, wherein 0.1.ltoreq.n.ltoreq.0.3, 0.3 < x < 1,0 < y < 0.1, and the M element includes at least one of Na, mg, al, ca, ba, V, zn, ti, fe, co, cr, nb, W, mo, zr, ta and Hf. Thus, the energy density of the positive electrode active material can be further improved, and the gram capacity of the first active material is not less than 150mAh/g in the 2.5V-4.35V interval.
According to an embodiment of the present application, the chemical formula of the lithium-containing phosphate satisfies LiFe 1-a-bMnaQbPO4, wherein 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.0.1, 0.ltoreq.a+b.ltoreq.1, and the Q element includes at least one of transition metal elements other than Fe and Mn and non-transition metal elements. Thus, the safety performance of the positive electrode active material can be improved, and the manufacturing cost of the positive electrode active material can be reduced.
According to an embodiment of the present application, the mass fraction of the first active material in the positive electrode active material is 10wt% to 90wt%; further, the mass fraction of the first active material in the positive electrode active material is 25wt% to 90wt%. Thereby, the energy density and cycle life of the positive electrode active material can be further improved.
According to an embodiment of the application, the Dv50 of the first active material is 4 μm-10 μm. Thus, the compacted density of the positive electrode active material is advantageously increased.
According to an embodiment of the application, the Dv50 of the second active material is 0.5 μm-2 μm. Thus, the compacted density of the positive electrode active material is advantageously increased.
According to an embodiment of the application, the discharge voltage plateau of the positive electrode active material is 3.3V-3.8V. Thereby, the energy density of the positive electrode active material is advantageously increased.
In another aspect of the present application, the present application provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode active material layer, the positive electrode active material layer being located at one side of the positive electrode current collector, the positive electrode active material layer including the aforementioned positive electrode active material. Therefore, the positive electrode sheet has all the characteristics and advantages of the positive electrode active material, and is not described herein.
According to the embodiment of the application, the compacted density of the positive electrode plate is 2.5g/cm 3-3.1g/cm3. Thereby, it is advantageous to obtain a battery having a higher energy density.
In yet another aspect of the present application, a battery is provided that includes a positive electrode tab, the positive electrode tab being the positive electrode tab described above. Therefore, the battery has all the characteristics and advantages of the positive electrode plate, and the details are not repeated here.
In yet another aspect of the present application, an electrical device is provided that includes the aforementioned battery. Therefore, the power utilization device has all the characteristics and advantages of the battery and is not described in detail herein.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a schematic structure of a positive electrode sheet according to an embodiment of the present application;
FIG. 2 is a schematic view of a battery according to an embodiment of the present application;
fig. 3 is an exploded view of the battery of the embodiment of the present application shown in fig. 2;
Fig. 4 is a schematic view of a battery module according to an embodiment of the present application;
fig. 5 is a schematic view of a battery pack according to an embodiment of the present application;
fig. 6 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 5;
FIG. 7 is a schematic diagram of an electrical device using a battery as a power source according to an embodiment of the present application;
FIG. 8 is a charge-discharge curve of the first active material of example 1 of the present application;
FIG. 9 is a cycle life curve of inventive example 1, example 6, and comparative example 1.
Reference numerals illustrate:
1: a battery pack; 2: an upper case; 3: a lower box body; 4: a battery module; 5: a battery; 10: a positive electrode sheet; 11: a positive electrode current collector; 12: a positive electrode active material layer; 51: a housing; 52: an electrode assembly; 53: and a top cover assembly.
Detailed Description
Embodiments of the present application are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the application.
In one aspect of the present application, the present application provides a positive electrode active material comprising: the first active material comprises a lithium-rich manganese-based material, and the gram capacity of the first active material in a 2.5V-4.35V range is not less than 150mAh/g; and a second active material including a lithium-containing phosphate. Thus, a positive electrode active material having a high gram capacity, a long cycle life, and a high energy density can be obtained. Gram capacity refers to the ratio between the amount of capacitance that an active material can release and the mass of the active material, with higher gram capacity indicating greater capacitance per mass of active material.
For ease of understanding, the following description will be given of the principle that the positive electrode active material in the present application has the above advantageous effects:
The lithium-containing phosphate positive electrode active material has the advantages of low cost, high safety and the like, and has the defects of low gram capacity and rapid early-stage cycle attenuation. For example, in the first charge and discharge process of the battery cell, the electrolyte solution undergoes a reduction decomposition reaction on the surface of the negative electrode, and forms a solid electrolyte interface film (SEI film), and the generation of the SEI film consumes a large amount of active lithium, thereby resulting in a decrease in the actual energy density of the battery compared with the theoretical calculation value. In the cycling process of the battery core, the cracking and crushing of lithium-containing phosphate particles, the thickening and repairing of the SEI film can continuously consume active lithium, so that the cycling performance of the battery is obviously reduced.
Further, although the lithium supplementing additive is added into the positive electrode active material layer, lithium can be added into the battery before the lithium battery works so as to supplement lithium ions, and the problems of low energy density, low first-ring efficiency, poor cycle life and the like of the lithium battery are solved. However, the lithium-supplementing additive in the related art usually needs to be charged to a higher voltage to effectively exert the lithium-supplementing capacity, and taking the lithium-rich manganese-based material as an example, the lithium-rich manganese-based material can bring about the advantages of high capacity, high energy density, low cost, long cycle life and the like due to the superlattice formed by the lithium-rich lithium manganate and the layered lithium metal oxide. However, the lithium-rich manganese-based material in the related art needs to be charged to 4.5V to effectively exert the capacity, thereby achieving the effect of lithium supplementation, and the working voltage of the lithium-containing phosphate is lower, typically 3.2-4.2V. If the lithium-containing phosphate is mixed with the lithium-supplementing additive with the upper limit voltage of more than 4.5V to form the positive electrode active material layer, after the battery is charged to 4.5V, the structure of the lithium-containing phosphate collapses, so that lithium ions cannot be intercalated back, thereby causing rapid attenuation of the capacity and obviously reducing the cycle performance of the battery.
According to the application, the lithium-rich manganese-based material with the gram capacity of not less than 150mAh/g in the 0.33C charging and discharging range of 2.5-4.35V is used as the lithium supplementing additive, and is mixed with the lithium-containing phosphate to be used as the positive electrode active material, so that the energy density (energy density=gram capacity×voltage plateau×compacted density) of the lithium-containing phosphate can be greatly improved, and the lithium-rich manganese-based material with the gram capacity of not less than 150mAh/g in the 0.33C charging and discharging range of 2.5-4.35V can be activated gradually under low voltage, active lithium is released in the circulating process, the consumption of anode lithium is supplemented, the early-circulating attenuation trend of a phosphate system is improved, and slow attenuation is realized. In summary, by utilizing the high capacity and high voltage characteristics of the lithium-rich manganese-based material and combining the advantages of low cost, high safety and the like of the lithium-containing phosphate particles, the energy density, the cycle stability and other electrical properties of the lithium-containing phosphate system are greatly improved, and the positive electrode active material with higher gram capacity, better cycle life and higher energy density is obtained. In general, by adopting the lithium-rich manganese-based material with the gram capacity of not less than 150mAh/g in the 0.33C charging and discharging range of 2.5-4.35V and the lithium-containing phosphate to be mixed and then used as the positive electrode active material of the lithium battery, the high-capacity and high-voltage characteristics of the lithium-rich manganese-based material are utilized to be combined with the advantages of low cost, high safety and the like of the lithium-containing phosphate particles, the electrical properties such as the energy density, the cycle stability and the like of a lithium-containing phosphate system are greatly improved, and the positive electrode active material with higher capacity, better cycle life and higher energy density is obtained.
In the description of the application, a "first feature" or "second feature" may include one or more of such features.
According to some embodiments of the application, the first active material is a lithium-rich manganese-based material, and the first active material may have a chemical formula satisfying nLi 2MnO3·(1-n)LiNixMn(1-x-y)MyO2, wherein 0.1.ltoreq.n.ltoreq.0.3, 0.3 < x < 1,0 < y < 0.1, and M element including at least one of Na, mg, al, ca, ba, V, zn, ti, fe, co, cr, nb, W, mo, zr, ta and Hf. The element M doped with the lithium-rich manganese-based material can promote the diffusion of lithium ions in the first active material, and through enhancing the dynamic performance of the first active material, the gram capacity of the lithium-rich manganese-based material is promoted, so that the capacity of a battery is improved, the manganese element can also improve the crystal structure stability of the lithium-rich manganese-based material, no obvious structural change occurs in the charging and discharging process, and the capacity, the circulation stability and the circulation life of the lithium-rich manganese-based material are improved. Specifically, liNi xMn(1-x-y)MyO2 in the first active material is an electrochemical active ingredient, and can release capacity during a cycle, li 2MnO3 in the first active material is an inactive ingredient, and plays a role in stabilizing the chemical structure of LiNi xMn(1-x-y)MyO2 during a cycle, and by controlling the proportion of Li 2MnO3 in the first active material to be 0.1-0.3, the gram capacity of the first active material at a range of 2.5V-4.35V is not less than 150mAh/g, for example, referring to fig. 8, when the chemical formula of the first active material is 0.2Li 2MnO3·0.8LiNi0.5Mn0.5O2, the gram capacity of the first active material when charged to 4.35V can be made to be greater than 155mAh/g. When the chemical formula of the first active material meets nLi 2MnO3·(1-n)LiNixMn(1-x-y)MyO2 and n is smaller than 0.1, the structure of the first active material is unstable, and the circulation stability of active ingredients in the first active material is poor; when the chemical formula of the first active material meets nLi 2MnO3·(1-n)LiNixMn(1-x-y)MyO2 and n is larger than 0.3, the gram capacity of the first active material is lower, the lithium supplementing effect is poorer, and the energy density of the lithium-containing phosphate system is not obviously improved.
According to some embodiments of the application, the second active material is a lithium-containing phosphate, in particular, the second active material may comprise an olivine-type lithium-containing phosphate. The kind of the lithium-containing phosphate is not particularly limited, and for example, the chemical formula of the lithium-containing phosphate may satisfy LiFe 1-a-bMnaQbPO4, wherein 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.0.1, 0.ltoreq.a+b.ltoreq.1, and the q element includes at least one of transition metal elements other than Fe and Mn and non-transition metal elements. Specifically, the lithium-containing phosphate may include at least one of lithium iron phosphate, lithium manganese phosphate, modified lithium iron phosphate, modified lithium manganese phosphate, and modified lithium manganese phosphate. The modifying compound of each material can be doping modification and/or surface coating modification of the material. The lithium-containing phosphate has the advantages of low cost, better test results of drop tests and needling tests and higher thermal safety during overcharging, and can effectively reduce the possibility of dangers during thermal abuse and mechanical abuse of the battery cell.
According to some embodiments of the present application, the mixing ratio of the first active material and the second active material in the positive electrode active material is not particularly limited, for example, the mass fraction of the first active material in the positive electrode active material may be 10wt% to 90wt%; further, the mass fraction of the first active material in the positive electrode active material may be 25wt% to 90wt%. When the content of the first active material in the positive electrode active material is within the above range, the content of the first active material in the positive electrode active material is higher, and the energy density of the positive electrode active material can be effectively improved.
According to some embodiments of the present application, the particle sizes of the first active material and the second active material are not particularly limited, for example, the Dv50 of the first active material may be 4 μm to 10 μm; further, the Dv50 of the first active material may be 6-8 μm; the Dv50 of the second active material may be 0.5 μm to 2 μm; further, the Dv50 of the second active material may be 0.8 to 1.5 μm, and when the Dv50 of the first active material and the second active material are within the above range, the gradation of particles may be achieved, further improving the compacted density of the positive electrode active material. The Dv50 of the particles may be measured using a laser particle sizer, specifically, the positive electrode active material powder particles are first dispersed in a suitable amount of solvent to form a dispersion. And then placing the dispersion liquid into a laser particle analyzer to measure the particle size of the anode active material powder.
According to some embodiments of the present application, a discharge voltage plateau of the mixed positive electrode active material may be 3.3V to 3.8V by mixing a lithium-rich manganese-based material having an upper charge voltage of not more than 4.5V with a lithium-containing phosphate having an upper charge voltage of not more than 4.2V in the aforementioned ratio. Specifically, the discharge voltage plateau of the positive electrode active material can be tested as follows: the positive electrode active material is manufactured into a battery through a conventional process, after the residual electric quantity in the battery is emptied, the battery is charged to respective upper limit voltage according to 1/3C, then the battery is charged to the current of less than or equal to 0.05C at constant voltage at the upper limit voltage, after standing for 5min, the battery is discharged to the voltage of 2.5V at 1/3C, the electric quantity discharged by the battery in the discharging process is the discharge capacity, and the energy output by the battery in the discharging process is the discharge energy through the formula: discharge voltage plateau = discharge energy/discharge capacity, the discharge voltage plateau can be calculated. With the increase of the proportion of the lithium-rich manganese-based material in the mixed positive electrode active material, the discharge voltage platform of the positive electrode active material is gradually raised. When the discharge voltage plateau of the positive electrode active material is within the aforementioned range, the mixed positive electrode active material including the lithium-rich manganese-based material and the lithium-containing phosphate mixed in the aforementioned ratio according to the present application has a higher energy density than the single lithium-containing phosphate positive electrode active material (voltage plateau of about 3.2V).
In the present application, all numbers disclosed herein are approximate, whether or not the word "about" or "about" is used. The numerical value of each number may vary by less than 10% or reasonably as considered by those skilled in the art, such as 1%, 2%, 3%, 4% or 5%. In another aspect of the present application, referring to fig. 1, the present application proposes a positive electrode tab 10 including a positive electrode current collector 11 and a positive electrode active material layer 12, the positive electrode active material layer 12 being located at one side of the positive electrode current collector 11, the positive electrode active material layer 12 including the aforementioned positive electrode active material. As an example, the positive electrode current collector 11 has two surfaces opposing in its own thickness direction, and the positive electrode active layer 12 may be provided on either or both of the two surfaces opposing the positive electrode current collector 11. Therefore, the positive electrode sheet comprises all the characteristics and advantages of the positive electrode active material, and the details are not repeated here.
According to some embodiments of the present application, a conventional metal foil or a composite current collector may be used as the positive electrode current collector (a metal material may be disposed on a polymeric substrate to form a composite current collector). For example, the positive electrode current collector may employ aluminum foil.
In yet another aspect of the present application, the present application provides a battery comprising: the positive pole piece is the positive pole piece. Typically, a battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film. Thus, the battery has a higher energy density and a superior capacity retention rate.
According to some embodiments of the present application, the shape of the battery is not particularly limited, and may be cylindrical, square, or any other shape. For example, fig. 2 is a square-structured battery 5 as an example. Specifically, referring to fig. 3, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is packaged in the receiving chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the battery 5 may be one or more, and those skilled in the art may choose according to specific practical requirements.
In the description of the present application, "plurality" means two or more.
According to some embodiments of the application, the battery may include an outer package. The outer package is used for packaging the positive electrode plate, the negative electrode plate and the electrolyte. For example, the outer package may include a housing and a cover. Wherein, the casing can include the bottom plate and connect the curb plate on the bottom plate, and bottom plate and curb plate enclose and close and form the chamber that holds. The shell is provided with an opening communicated with the accommodating cavity, and the cover plate can cover the opening to seal the accommodating cavity. The positive electrode sheet, the negative electrode sheet and the separator may be formed into an electrode assembly through a winding process or a lamination process. The electrode assembly is encapsulated in the accommodating cavity. The electrolyte may be an electrolyte solution, which is impregnated in the electrode assembly. The number of electrode assemblies included in the battery may be one or several, and may be adjusted according to the needs.
According to some embodiments of the present application, the cells may be assembled into a battery module, and the number of cells contained in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module. Fig. 4 is a battery module 4 as an example. Referring to fig. 4, in the battery module 4, a plurality of batteries 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of batteries 5 may be further fixed by fasteners. The battery module 4 may further include a case having an accommodating space in which the plurality of batteries 5 are accommodated.
According to some embodiments of the present application, the battery modules may be assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack. Fig. 5 and 6 are battery packs 1 as an example. Referring to fig. 5 and 6, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
According to some embodiments of the present application, by mixing a first active material having a Dv50 of 4 μm to 10 μm with a second active material having a Dv50 of 0.5 μm to 2 μm in the above-described ratio, the compacted density of the positive electrode tab may be 2.5g/cm 3-3.1g/cm3, and when the compacted density of the positive electrode tab is within the above-described range, the battery including the above-described positive electrode tab has a higher energy density.
In yet another aspect of the present application, the present application provides an electric device, comprising: the aforementioned battery. The battery, battery module, or battery pack may be used as a power source for the electrical device, and may also be used as an energy storage unit for the electrical device. The power utilization device may include, but is not limited to, mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, and the like. The power utilization device can select a battery, a battery module or a battery pack according to the use requirement thereof.
Fig. 7 is an electrical device as an example, according to some embodiments of the application. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. To meet the high power and high energy density requirements of the power device for the battery, a battery pack or battery module may be employed.
According to some embodiments of the present application, the power consumption device may also be a mobile phone, a tablet computer, a notebook computer, or the like. The device is generally required to be light and thin, and a battery can be used as a power source.
The following description of the present application is made by way of specific examples, which are given for illustration of the present application and should not be construed as limiting the scope of the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
The synthesis method of the first active material comprises the following steps:
Manganese sulfate is used as a manganese source, nickel sulfate is used as a nickel source, and a transition metal salt solution is prepared according to the mole ratio of Mn to Ni elements of 6:4, and the concentration of the solution is 2mol/L. Preparing sodium carbonate solution with the concentration of 2mol/L and preparing ammonia water solution with the concentration of 1 mol/L. Adding deionized water with 20% of the volume of the reaction kettle as a reaction base solution into the reaction kettle, respectively pumping a transition metal salt solution, a sodium carbonate solution and an ammonia water solution into the reaction kettle at the flow rate of V 1＝35mL/h、V2＝5-50mL/h、V3 = 35mL/h under the protection of nitrogen atmosphere, controlling the pH value of the reaction system to be = 9.5 by adjusting the feeding flow rate V 2 of the sodium carbonate solution, and reacting for 20h under the condition of maintaining the temperature of the reaction system to be 50 ℃ and the stirring speed to be 800 rpm. And (3) aging the reaction slurry for 10 hours after the feeding is finished, and filtering, washing and drying the precipitate to obtain a first active material precursor Ni 0.4Mn0.6CO3. And finally, uniformly mixing the precursor powder of the first active material with a lithium source (lithium carbonate) according to the weight ratio of 100:50, and sintering for 8 hours at 800 ℃ in an air atmosphere to obtain the first active material.
Determination of the chemical formula of the first active material: by inductively coupled plasma emission spectroscopy. Specifically, the first active material is digested by aqua regia, and then the obtained aqua regia solution containing the first active material is introduced into an inductively coupled plasma emission spectrometer to obtain the absolute content of each element in the first active material, so as to obtain the chemical composition.
The chemical formula of the first active material is 0.2Li 2MnO3·0.8LiNi0.5Mn0.5O2, and the second active material is lithium iron phosphate, wherein the mass ratio of the first active material in the mixed positive electrode active material is 50wt%, and the rest is the second active material.
Preparation of a lithium ion battery:
1. Preparation of positive electrode plate
The positive electrode active material, the conductive agent acetylene black and the binder PVDF (polyvinylidene fluoride) are mixed according to the weight ratio of 94:4:2, mixing, adding solvent N-methyl pyrrolidone, and fully stirring and uniformly mixing to obtain the positive electrode slurry. And (3) coating the positive electrode slurry on two surfaces of a positive electrode current collector aluminum foil, and drying and cold pressing to obtain a positive electrode plate.
2. Preparation of negative electrode plate
Artificial graphite, conductive agent acetylene black, binder SBR (styrene butadiene rubber) and binder CMC (sodium carboxymethyl cellulose) are mixed according to the weight ratio of 95:1.5:3.1: and 0.4, mixing, adding deionized water serving as a solvent, and fully stirring and uniformly mixing to obtain the negative electrode slurry. And (3) coating the negative electrode slurry on two surfaces of a negative electrode current collector copper foil, drying, and cold pressing to 1.65g/cm 3 to obtain a negative electrode plate.
3. Preparation of electrolyte
EC (ethylene carbonate), PC (polycarbonate), DMC (dimethyl carbonate) were mixed in weight ratio EC in an argon atmosphere glove box with a water content of <10 ppm: PC: dmc=3: 3:3, then adding LiPF 6, VC (vinylene carbonate), DTD (vinyl sulfate) and PS (1, 3-propane sultone), stirring uniformly to obtain an electrolyte, wherein the concentration of LiPF 6 in the electrolyte is 1mol/L, and the mass percentages of VC, DTD and PS are 3wt%,1wt% and 1wt% respectively.
4. Preparation of a separator film
A polyethylene porous film was used as a separator.
5. Preparation of lithium ion batteries
Sequentially stacking the prepared positive electrode plate, the isolation film and the negative electrode plate, so that the isolation film is positioned between the positive electrode plate and the negative electrode plate to play a role in isolation, and a bare cell is obtained; and placing the bare cell in an outer package, injecting the prepared electrolyte, and packaging to form the lithium ion battery.
Example 2:
In keeping with example 1, except that the first active material was synthesized by preparing a transition metal salt solution at a molar ratio of Mn to Ni of 6.6:3.4; the chemical formula of the first active material is 0.3Li 2MnO3·0.7LiNi0.5Mn0.5O2.
Example 3:
In keeping with example 1, except that the first active material was synthesized by preparing a transition metal salt solution at a molar ratio of Mn to Ni of 5.5:4.5; the chemical formula of the first active material is 0.1Li 2MnO3·0.9LiNi0.5Mn0.5O2.
Example 4:
in keeping with example 1, except that the mass ratio of the first active material in the positive electrode active material was 30wt%.
Example 5:
in keeping with example 1, the first active material was present at a mass ratio of 70wt% in the positive electrode active material.
Example 6:
In keeping with example 1, except that the mass ratio of the first active material in the positive electrode active material was 90wt%.
Comparative example 1:
in keeping with example 1, except that the positive electrode active material was lithium iron phosphate.
The batteries of examples 1 to 6 and comparative example 1 were subjected to the following test, and the test results are shown in Table 1.
1. Battery capacity test:
Discharging the batteries of each example and comparative example to 2.5V at 1/3C under a constant temperature environment at 25 ℃ to empty the residual electric quantity in the batteries, standing for 5min, charging to respective upper limit voltages according to 1/3C, then charging to current less than or equal to 0.05C at constant voltage at the upper limit voltages, standing for 5min, discharging to 2.5V at 1/3C, wherein the electric quantity discharged by the batteries in the discharging process is discharge capacity, the energy output by the batteries in the discharging process is discharge energy, and recording a discharge voltage platform, and the specific calculation method comprises the following steps: and recording the discharge energy of the battery in the discharge process, and dividing the discharge energy by the discharge capacity to obtain a discharge voltage platform.
2. And (3) testing the cycle performance:
charging to upper limit voltage with constant current of 1C under constant temperature environment of 25deg.C, then charging to current reduced to 0.05C with constant voltage of upper limit voltage, and discharging to 2.5V with constant current of 1C to obtain first week discharge specific capacity (C0); the charge and discharge were repeated for 1000 weeks to obtain a specific discharge capacity after 1000 weeks of cycle, which was denoted as Cn.
Capacity retention = specific discharge capacity after 1000 weeks (C n)/specific discharge capacity at first week (C 0).
The positive electrode active materials in examples 1 to 6 and comparative example 1 were subjected to the following test, and the test results are shown in table 1.
1. The testing method of the compaction density of the positive pole piece comprises the following steps: firstly, measuring the thickness T of the rolled positive pole piece, and then calculating the compaction density rho Pressing according to the surface density, wherein the calculation formula is as follows: ρ Pressing ＝m/(T-T Foil sheet ), wherein m is the areal density of the pole piece, the unit is g/cm 2,T Foil sheet is the thickness of the negative current collector, and the unit is cm.
2. Test method of gram capacity of positive electrode active material: and dividing the measured battery capacity by the mass of the positive electrode active material to obtain the gram capacity of the positive electrode active material.
3. Test method for gram capacity of first active material: positive electrode active materials including only the positive electrode sheets of the first active materials in examples 1 to 6 were prepared, respectively, and batteries were fabricated with reference to the above steps, and the battery capacities were tested, wherein the upper charge voltages were referred to table 1, and the gram capacities of the first active materials were obtained by dividing the measured battery capacities by the added mass of the first active materials in the positive electrode sheets.
TABLE 1
The test result shows that by utilizing the high capacity and high voltage characteristics of the lithium-rich manganese-based material and combining the advantages of low cost, high safety and the like of the lithium-containing phosphate particles, the energy density, the cycling stability and other electrical properties of the lithium-containing phosphate system are greatly improved, and the positive electrode active material with higher gram capacity, better cycling life and higher energy density is obtained.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The terms "comprising" or "including" are used in an open-ended fashion, i.e., including the teachings described herein, but not excluding additional aspects.
In the description of the present specification, reference to the term "one embodiment," "another embodiment," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (11)
1. A positive electrode active material, characterized by comprising:
A first active material comprising a lithium-rich manganese-based material, the first active material having a gram capacity of not less than 150mAh/g in the range of 2.5V-4.35V;
A second active material comprising a lithium-containing phosphate.
2. The positive electrode active material according to claim 1, wherein a chemical formula of the first active material satisfies nLi 2MnO3·(1-n)LiNixMn(1-x-y)MyO2, wherein 0.1.ltoreq.n.ltoreq.0.3, 0.3 < x <1, 0 < y < 0.1, and the M element includes at least one of Na, mg, al, ca, ba, V, zn, ti, fe, co, cr, nb, W, mo, zr, ta and Hf.
3. The positive electrode active material according to claim 1, wherein a chemical formula of the lithium-containing phosphate satisfies LiFe 1-a-bMnaQbPO4, wherein 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.0.1, 0.ltoreq.a+b.ltoreq.1, and the Q element includes at least one of transition metal elements other than Fe and Mn and non-transition metal elements.
4. The positive electrode active material according to claim 1, wherein a mass fraction of the first active material in the positive electrode active material is 10wt% to 90wt%; preferably, the mass fraction of the first active material in the positive electrode active material is 25wt% to 90wt%.
5. The positive electrode active material according to claim 1, wherein the first active material has a Dv50 of 4 μm to 10 μm.
6. The positive electrode active material according to claim 1, wherein the Dv50 of the second active material is 0.5 μm to 2 μm.
7. The positive electrode active material according to any one of claims 1 to 6, wherein a discharge voltage plateau of the positive electrode active material is 3.3V to 3.8V.
8. A positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer, the positive electrode active material layer being located on one side of the positive electrode current collector, the positive electrode active material layer comprising the positive electrode active material according to any one of claims 1 to 7.
9. The positive electrode sheet according to claim 8, wherein the compacted density of the positive electrode sheet is 2.5g/cm 3-3.1g/cm3.
10. A battery comprising a positive electrode sheet comprising the positive electrode sheet of claim 8 or 9.
11. An electric device is characterized in that, the power utilization device comprises the battery of claim 10.
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