CN115360423A - Method for improving electrical property of metal secondary battery - Google Patents
Method for improving electrical property of metal secondary battery Download PDFInfo
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- CN115360423A CN115360423A CN202211144352.5A CN202211144352A CN115360423A CN 115360423 A CN115360423 A CN 115360423A CN 202211144352 A CN202211144352 A CN 202211144352A CN 115360423 A CN115360423 A CN 115360423A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title description 3
- 239000002184 metal Substances 0.000 title description 3
- 239000000654 additive Substances 0.000 claims abstract description 51
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 46
- 239000007772 electrode material Substances 0.000 claims abstract description 38
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 38
- 239000002516 radical scavenger Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims description 16
- -1 ester compounds Chemical class 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011366 tin-based material Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002001 electrolyte material Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 229910013872 LiPF Inorganic materials 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Abstract
The invention discloses a new method for improving the performance of a metal ion secondary battery, which is based on a moisture scavenger MP 3 O 10 As additive for organic electrolyte or/and electrode material, wherein MP 3 O 10 The additive can be hydrated with residual moisture in the organic electrolyte or/and the electrode material to generate MP 3 O 10 ·nH 2 The O hydrate can effectively inhibit the organic electrolyte from decomposing when encountering water, avoid the decomposition of the electrolyte to generate acidic substances such as HF and the like and prevent the acidic substances from corroding the surface of the electrode material, improve the structural stability of the electrode material and improve the cycle life of the secondary battery. Meanwhile, the method has simple steps, is easy to control and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of metal ion secondary batteries, and particularly relates to a moisture scavenger MP 3 O 10 A novel method for improving the performance of a secondary battery as an additive of an organic electrolyte or/and an electrode material.
Background
The information in this background section is only for enhancement of some understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Renewable clean energy sources such as solar energy, wind energy and the like have obvious intermittency, volatility and randomness, and an efficient and low-cost electrochemical energy storage technology is an important basis for wide application of the renewable clean energy sources. The secondary battery is used as a rechargeable battery, and has longer service life and longer endurance compared with a common primary battery. Among many secondary batteries, high energy density lithium ion batteries have been widely commercialized and widely used in the fields of portable electronic devices, electric vehicles, and the like. In addition to this, various novel metal ion secondary batteries (sodium ion batteries, potassium ion batteries, lithium sulfur batteries, and the like) are widely studied. The metal ion secondary battery may be mainly classified into an alkali metal ion battery, a polyvalent metal ion battery, a metal-air battery, a metal-sulfur battery, and the like. The secondary battery is similar in construction and composition, and is mainly composed of a positive electrode, a negative electrode, an electrolyte, a separator, and a casing material.
Electrode materials are undoubtedly the focus of attention and research by researchers. At the same time, however, the electrolyte is also a non-negligible aspect, and functions to conduct ions between the positive and negative electrodes in the battery. The electrolyte is mainly divided into two major categories, namely a water system and a non-water system (an organic system), wherein the organic system can ensure high working voltage and give consideration to the performances such as energy density, rate capability, cycling stability and the like, and is the electrolyte system mainly applied to the current commercial secondary battery. The organic electrolyte is generally prepared from raw materials such as a high-purity organic solvent, an electrolyte salt, necessary additives and the like according to a certain proportion under certain conditions.
Commercial lithium ion batteries mostly use liquid organic electrolytes, and generally consist of lithium salts, additives, and solvents such as Ethylene Carbonate (EC), dimethyl carbonate (DMC), diester carbonate (DEC), or ethylmethyl carbonate (EMC). The common lithium salt is LiPF 6 And LiClO 4 . However, a very small amount of residual moisture of the organic electrolyte may react with the lithium salt to generate HF or HClO 4 Moderately strong acids, HF or HClO in electrochemical reactions 4 H is generated by side reaction with the surface of the oxide electrode 2 And O, further accelerating the decomposition of the electrolyte and the side reaction and structural degradation of the electrode surface, and finally causing the rapid decline of the capacity and the service life of the battery.
Disclosure of Invention
In order to suppress the decomposition of the electrolyte and the side reaction between the electrode and the electrolyte caused by the residual moisture, improve the cycling stability and the service life of the battery and meet the requirements of the market on the performance of the battery against the above background technologies, the inventors have made extensive research and exploration and have proposed a moisture scavenger MP 3 O 10 The new method for improving the performance of the secondary battery as the additive of the organic electrolyte or/and the additive of the electrode material.
Specifically, the invention adopts the following technical scheme:
in a first aspect of the invention, a moisture scavenger MP is provided 3 O 10 New method for improving performance of secondary battery as additive of organic electrolyte or/and electrode material, wherein MP 3 O 10 The additive can be hydrated with residual moisture in the organic electrolyte or/and the electrode material to generate MP 3 O 10 ·nH 2 The O hydrate can effectively inhibit the organic electrolyte from decomposing when encountering water, so that acidic substances such as HF and the like generated by the decomposition of the electrolyte and the corrosion of the acidic substances on the surface of the electrode material are avoided, the structural stability of the electrode material is improved, and the cycle life of a secondary battery is prolonged; the method comprises the following steps:
the moisture scavenger MP with set mass 3 O 10 Adding the functional electrolyte into organic electrolyte as an additive to form functional electrolyte; and/or a moisture scavenger MP of a set mass 3 O 10 Uniformly mixing the additive serving as an additive with an electrode material to form a composite electrode material; wherein M is Li + 、Na + 、K + 、NH 4 + 、Mg 2+ 、Al 3+ 、H + One or more cations or groups formed so that the total valence of the M ion is +5.
In one or some embodiments of the present invention, the solute of the organic electrolyte includes one or more of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, and aluminum salt.
In one or some embodiments of the present invention, the solvent of the organic electrolyte includes one or more of an ester compound, an ether compound, an amide compound, a sulfone compound, and a nitrile compound.
In one or some embodiments of the invention, the electrode material comprises a positive electrode and a negative electrode, wherein the positive electrode is one or more of an oxide, a phosphate, and prussian blue, and the negative electrode material is one or more of a carbon-based material, a silicon/carbon composite material, a tin-based material, and a lithium titanate material.
In one or some embodiments of the invention, the metal ion secondary battery is one or more of a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery, a zinc ion battery, an aluminum ion battery, a lithium-sulfur battery, a lithium-oxygen battery.
In one or some embodiments of the invention, in the functional electrolyte, MP 3 O 10 The mass fraction of the additive is 0.01-3wt.%; a large number of experiments prove that the additive with the mass fraction exceeding 3wt.% can improve the viscosity of the electrolyte and prevent lithium ions from migrating in the electrochemical reaction; the mass fraction of the additive is less than 0.01wt.% so that the additive does not react sufficiently with the residual moisture of the electrolyte and the electrical property improving effect is not good enough.
Preferably, MP 3 O 10 The mass fraction of the additive is 0.1-0.8wt.%.
In one or some embodiments of the invention, in the composite electrode material, MP 3 O 10 The mass fraction of the additive is 0.01-5wt.%; through a large number of experiments, the mass fraction of the additive exceeding 5wt.% can reduce the specific capacity and the electrode density of the composite electrode material, and reduce the energy density of the lithium ion battery; a mass fraction of the additive of less than 0.01wt.% results in insufficient reaction between the additive and the residual moisture on the surface of the electrode, and poor electrical property improvement effect.
Preferably, MP 3 O 10 The mass fraction of the additive is 0.3-1.5wt.%.
In a second aspect of the invention, a moisture scavenger MP is provided, which is prepared by the above method 3 O 10 Added into organic electrolyte or composite electrode material as additiveAnd (4) feeding.
In a third aspect of the present invention, there is provided a moisture scavenger MP comprising the moisture scavenger MP 3 O 10 And a metal ion secondary battery as an additive to be added to the organic electrolyte or the composite electrode material, the metal ion secondary battery comprising the composite electrode material, a functional organic electrolyte, a separator, and the like.
Compared with the related technologies known by the inventor, one technical scheme of the invention has the following beneficial effects:
the invention firstly provides a moisture scavenger MP 3 O 10 Functional electrolyte as organic electrolyte additive, and moisture scavenger MP 3 O 10 As additive combined with electrode material, wherein MP 3 O 10 The additive can be hydrated with residual moisture in the organic electrolyte or/and the electrode material to generate MP 3 O 10 ·nH 2 The O hydrate can effectively inhibit the organic electrolyte from decomposing when encountering water, avoid the decomposition of the electrolyte to generate acidic substances such as HF and the like and prevent the acidic substances from corroding the surface of the electrode material, improve the structural stability of the electrode material and improve the cycle life of the secondary battery. Meanwhile, the method has simple steps, is easy to control and is suitable for large-scale industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the cycle profiles of lithium ion batteries prepared in example 1 and comparative example 1;
FIG. 2 is a graph showing the cycle profiles of the lithium ion batteries prepared in example 4 and comparative example 1;
FIG. 3 is a graph showing the cycle profiles of the sodium ion batteries prepared in example 5 and comparative example 2;
fig. 4 cycle profiles of the sodium ion batteries prepared in example 5 and comparative example 3.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should also be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the features, steps, operations and/or combinations thereof.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Comparative example 1: lithium ion full battery performance based on conventional electrolyte assembly
With a single-crystal layered oxide Li [ Ni ] 0.6 Co 0.1 Mn 0.3 ]O 2 (NCM 613) is a positive electrode, the mesocarbon microbeads are a negative electrode and organic electrolyte (1M LiPF) 6 Dissolving in EC and DMC solvent, and assembling the lithium ion full battery according to the volume ratio of 3). The cycling stability of the lithium ion full cell was tested at room temperature (25 ℃) at a voltage range of 2.5-4.4V and a current density of 100 mA/g.
Example 1: based on Li content 5 P 3 O 10 Additive electrolyte assembled lithium ion full cell performance
0.5g of Li was weighed 5 P 3 O 10 100g of an organic electrolyte (1M LiPF) was added 6 Dissolving in EC and DMC solvent, and stirring for 2h to form a functional electrolyte solution. The positive electrode and the negative electrode in comparative example 1 and the Li-containing material prepared 5 P 3 O 10 And (4) assembling the lithium ion full cell by the functional electrolyte of the additive. The cycling stability of the lithium ion full cell was tested at a voltage range of 2.5-4.4V, a current density of 100mA/g and room temperature (25 ℃). Testing the water content of the electrolyte/anode material and the electrolyte after different storage time and cycle numberPositive electrode material pH (HF content).
Example 2: based on containing K 5 P 3 O 10 Additive electrolyte assembled lithium ion full cell performance
0.7g of K are weighed out 5 P 3 O 10 100g of an organic electrolyte (1M LiPF) was added 6 Dissolving in EC and DMC solvent, and stirring for 2h to form a functional electrolyte solution, wherein the volume ratio is 3). The positive electrode and the negative electrode in comparative example 1 and the prepared K-containing material 5 P 3 O 10 And (4) assembling the lithium ion full battery by using the additive functional electrolyte. The electrolyte/anode material water content, electrolyte/anode material pH (HF content) were tested after various storage times and cycle cycles.
Example 3: based on (NH) 4 ) 5 P 3 O 10 Lithium ion full battery performance assembled by additive electrolyte
0.3g (NH) is weighed 4 ) 5 P 3 O 10 Added to 100g of an organic electrolyte (1M LiPF) 6 Dissolving in EC and DMC solvent, and stirring for 2h to form a functional electrolyte solution. The positive electrode and the negative electrode in comparative example 1 and prepared organic compound containing (NH) 4 ) 5 P 3 O 10 And (4) assembling the lithium ion full cell by the functional electrolyte of the additive. The electrolyte/positive material water content, electrolyte/positive material pH (HF content) were tested after different storage times and cycle weeks.
Example 4: based on containing MgH 3 P 3 O 10 Lithium ion full battery performance assembled by additive and NCM613 composite positive electrode
Weighing 1.5g MgH 3 P 3 O 10 The additive is added into 100g of NCM613 cathode material and uniformly mixed to form the composite cathode material. A lithium ion full cell was assembled with the negative electrode, the organic electrolyte and the composite positive electrode material in comparative example 1. The cycling stability of the lithium ion full cell was tested at room temperature (25 ℃) at a voltage range of 2.5-4.4V and a current density of 100 mA/g. The electrolyte/positive material water content, electrolyte/positive material pH (HF content) were tested after different storage times and cycle weeks.
Comparative example 2: conventional sodium ion full cell performance
In the P2 phase Na 2/3 [Ni 1/3 Mn 2/3 ]O 2 Is a positive electrode, a hard carbon is a negative electrode and an organic electrolyte (1M NaPF) 6 Dissolving in EC and DEC solvents, and assembling the sodium ion full cell according to the volume ratio of 1). The cycling stability of the sodium ion full cell is tested in a voltage range of 1.5-4.3V, a current density of 50mA/g and a room temperature (25 ℃).
Example 5: based on Na 5 P 3 O 10 Sodium ion full battery performance of additive and P2 phase composite anode
Weighing 1.5g Na 5 P 3 O 10 Adding into 100g P2 phase Na 2/3 [Ni 1/3 Mn 2/3 ]O 2 And (3) uniformly mixing the positive electrode material to form the composite positive electrode material. A sodium ion full cell was assembled with the negative electrode, the organic electrolyte and the composite positive electrode material in comparative example 2. The cycling stability of the sodium ion full cell is tested in a voltage range of 1.5-4.3V, at a current density of 50mA/g and at room temperature (25 ℃). The electrolyte/positive material water content, electrolyte/positive material pH (HF content) were tested after different storage times and cycle weeks.
Example 6: based on AlH 2 P 3 O 10 Sodium ion full battery performance of additive and P2 phase composite anode
1.5g of AlH are weighed out 2 P 3 O 10 Adding into 100g P2 phase Na 2/3 [Ni 1/3 Mn 2/3 ]O 2 And (3) uniformly mixing the positive electrode material to form the composite positive electrode material. A sodium ion full cell was assembled with the negative electrode, the organic electrolyte and the composite positive electrode material in comparative example 2. The cycling stability of the sodium ion full cell is tested in a voltage range of 1.5-4.3V, a current density of 50mA/g and a room temperature (25 ℃). The electrolyte/positive material water content, electrolyte/positive material pH (HF content) were tested after different storage times and cycle weeks.
Example 7: based on Na 2 H 3 P 3 O 10 Sodium ion full battery performance of additive and P2 phase composite anode
0.5g of Na was weighed 2 H 3 P 3 O 10 Added to 100g of organic electrolyte (1M NaPF) 6 Dissolved in EC andDEC solvent, volume ratio 1). The positive electrode and the negative electrode in comparative example 2 and the prepared Na-containing material 2 H 3 P 3 O 10 And (4) assembling the sodium ion full cell by using the additive functional electrolyte. The electrolyte/positive material water content, electrolyte/positive material pH (HF content) were tested after different storage times and cycle weeks.
Comparative example 3: the difference from example 1 is: 1.5g of trimethylsilyl trifluoromethanesulfonate was weighed out and added to 100g of an organic electrolyte (1M LiPF) 6 Dissolved in EC and DMC solvent in a volume ratio of 3). The rest of the method and procedure were the same as in example 1.
The electrolyte moisture content and the electrolyte pH of the examples 1 to 7 and the comparative examples 1 to 3 were measured at different storage times; and electrolyte moisture content and electrolyte pH measurements at different cycle counts, the results are shown in tables 1 and 2. The lithium ion full cell cycle stability of examples 1, 4, 5, and 1-3 was tested at room temperature (25 ℃) at 100mA/g current density in a voltage interval of 2.5-4.4V.
TABLE 1 moisture content and pH test results of electrolyte/cathode materials at different storage times
Table 2 electrolyte/anode material moisture content and electrolyte/anode material pH test results under different cycle numbers
From tables 1 and 2, the additive MP in the present invention is compared with the conventional electrolyte or positive electrode material (including but not limited to the electrolyte or positive electrode material to which additives such as silicone grease compounds are added) 3 O 10 The method has good water removal effect in electrolyte and electrode materials, avoids acidic substances such as HF and the like generated by electrolyte decomposition and corrosion of the acidic substances to the surface of the electrode material, and improves the structural stability of the electrode material.
As can be seen from fig. 1 to 4, the additive MP in the present invention is compared to a metal secondary battery prepared from a conventional electrolyte or positive electrode material (including, but not limited to, an electrolyte or positive electrode material to which an additive such as a silicone-based compound is added) 3 O 10 The performance of the secondary battery prepared from the electrolyte and the electrode material has stronger battery cycle stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Moisture scavenger MP 3 O 10 A method for improving the performance of a secondary battery as an additive to an organic electrolyte or/and an electrode material, characterized in that MP 3 O 10 The additive can be hydrated with residual moisture in the organic electrolyte or/and the electrode material to generate MP 3 O 10 ·nH 2 The O hydrate can effectively inhibit the organic electrolyte from decomposing when encountering water, so that acidic substances generated by the decomposition of the electrolyte and the corrosion of the acidic substances to the surface of the electrode material are avoided, the structural stability of the electrode material is improved, and the cycle life of the secondary battery is prolonged; the method comprises the following steps:
the moisture scavenger MP with set mass 3 O 10 Adding the functional electrolyte into organic electrolyte as an additive to form functional electrolyte; and/or a moisture scavenger MP of a set mass 3 O 10 Uniformly mixing the additive serving as an additive with an electrode material to form a composite electrode material; wherein M is Li + 、Na + 、K + 、NH 4 + 、Mg 2+ 、Al 3+ 、H + One or more kinds of instituteThe cation or group formed satisfies that the total valence of the M ion is +5.
2. The method of claim 1, wherein the organic electrolyte solute comprises one or more of lithium, sodium, potassium, magnesium, calcium, and aluminum salts.
3. The method according to claim 1, wherein the solvent of the organic electrolyte includes one or more of ester compounds, ether compounds, amide compounds, sulfone compounds and nitrile compounds.
4. The method of claim 1, wherein the electrode materials comprise a positive electrode and a negative electrode, wherein the positive electrode is one or more of an oxide, a phosphate, and Prussian blue, and the negative electrode material is one or more of a carbon-based material, a silicon/carbon composite material, a tin-based material, and a lithium titanate material.
5. The method according to claim 1, wherein the metal ion secondary battery is one or more of a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery, a zinc ion battery, an aluminum ion battery, a lithium-sulfur battery, and a lithium-oxygen battery.
6. The method as set forth in claim 1, wherein in the functional electrolyte, MP 3 O 10 The mass fraction of the additive is 0.01-3wt.%;
preferably, MP 3 O 10 The mass fraction of the additive is 0.1-0.8wt.%.
7. The method of claim 1, wherein in the composite electrode material, MP 3 O 10 The mass fraction of the additive is 0.01-5wt.%.
8. The method as set forth in claim 7, wherein,MP 3 O 10 the mass fraction of the additive is 0.3-1.5wt.%.
9. An organic electrolyte or a composite electrode material prepared by the method of any one of claims 1 to 8.
10. A metal ion secondary battery comprising the organic electrolyte according to claim 9 and the composite electrode material according to claim 9.
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