TWI755656B - Electrolyte composition for aluminum-ion battery and aluminum-ion battery employing the same - Google Patents

Abstract

An electrolyte composition for alumnium-ion and an alumnium-ion battery employing the same are provided. The electrolyte composition includes a metal salt of Formula (I), an ionic liquid, and an additive.

M_iX_j Formula (I) , wherein M can be aluminum ion; X^- can be F^-, Cl^-, Br^-, I^-, BF₄, PF₆ ^-, [(CF₃SO₂)₂N]^-, CF₃SO₃ ^-, NO₃ ^-, CH₃CO₂ ^-, SO₄ ^2-, C₂O₄ ^2-, or [B(C₂O₄)₂]^-; and i is 1, 2, 3, 4, 5, or 6; and j is 1, 2, 3, 4, 5, or 6. The additive includes a substituted or unsubstituted C₅-C₃₀ nitrogen-containing heterocyclic compound.

Description

Electrolyte composition for aluminum ion battery and aluminum containing the same Ion battery

The present disclosure pertains to electrolyte compositions and metal-ion batteries comprising the same.

Electrolyte compositions used in conventional metal-ion batteries include ionic liquids. Taking aluminum ion batteries as an example, some aluminum ion batteries use aluminum chloride/imidazolium chloride as the electrolyte composition. Although the electrolyte composition of aluminum chloride/imidazolium chloride is traditionally used, it has good electrochemical reversibility, and stable charge-discharge cycles can be achieved in principle. However, after the battery has undergone multiple charge-discharge cycles and the negative electrode metal material has undergone multiple electrolysis/deposition cycles, the surface of the metal material often grows in a specific direction, resulting in the formation of dendrites on the surface, plus the self-destruction that occurs in contact with the ionic liquid. The corrosion effect causes the loss of the aluminum negative electrode after multiple charge-discharge cycles, which makes the battery cycle performance decline, resulting in a decline in battery life.

Therefore, the industry needs a new electrolyte composition to solve the above problems.

According to an embodiment of the present disclosure, the present disclosure provides an electrolyte composition comprising a metal salt having a structure represented by formula (I), an ionic liquid, and an additive. M _i X _j formula (I) wherein M is lithium ion, sodium ion, potassium ion, beryllium ion, magnesium ion, calcium ion, scandium ion, yttrium ion, titanium ion, zirconium ion, hafnium ion, vanadium ion, niobium ion , tantalum ion, chromium ion, molybdenum ion, tungsten ion, manganese ion, onium ion, rhenium ion, iron ion, ruthenium ion, osmium ion, cobalt ion, rhodium ion, iridium ion, nickel ion, palladium ion, platinum ion, copper ion ion, silver ion, gold ion, zinc ion, cadmium ion, mercury ion, indium ion, thallium ion, tin ion, lead ion, arsenic ion, antimony ion, bismuth ion, gallium ion, or aluminum ion; X series F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , CF ₃ SO ₃ ^- , NO ₃ ^- , CH ₃ CO ₂ ^- , SO ₄ ^2- , C ₂ O ₄ ^2- , or [B(C ₂ O ₄ ) ₂ ] ^- ; and, i is 1, 2, 3, 4, 5, or 6; j is 1, 2, 3, 4, 5, or 6. The additive contains substituted or unsubstituted _C5 - _C30 nitrogen-containing heterocyclic compounds.

According to an embodiment of the present disclosure, the present disclosure provides a metal ion battery. The metal ion battery may comprise a positive electrode, a separator, a negative electrode, and the above-mentioned electrolyte composition. Wherein, the negative electrode can be separated from the positive electrode by a separator, and the above-mentioned electrolyte composition can be arranged between the positive electrode and the negative electrode.

10‧‧‧Positive

11‧‧‧Anode collector layer

12‧‧‧Negative

13‧‧‧Positive active material

14‧‧‧Isolation film

20‧‧‧Electrolyte composition

100‧‧‧Metal ion battery

FIG. 1 is a schematic diagram of the metal ion battery disclosed in one embodiment;

Figures 2 to 4 are the original aluminum foil, the aluminum negative electrode of the metal ion battery (1) of Comparative Example 1 after 3000 charge-discharge cycles, and the metal ion battery (8) of Example 6 after 3000 charge-discharge cycles. Photographic photograph of the surface of the aluminum anode.

The electrolyte composition and metal ion battery described in the present disclosure will be described in detail below. It should be appreciated that the following description provides many different embodiments or examples for implementing different aspects of the present disclosure. The specific elements and arrangements described below are for the purpose of simply describing the present disclosure. Of course, these are only examples and not limitations of the present disclosure. Furthermore, repeated reference numbers or designations may be used in different embodiments. These repetitions are for simplicity and clarity of the present disclosure and do not imply any association between the different embodiments and/or structures discussed. In the drawings, the shapes, numbers, or thicknesses of the embodiments may be expanded and marked for simplification or convenience. Furthermore, the parts of each element in the drawings will be described and described separately. It is worth noting that the elements not shown or described in the drawings are in the form known to those of ordinary skill in the art. The embodiments are only intended to disclose specific ways of using the present disclosure, and are not intended to limit the present disclosure.

The present disclosure provides an electrolyte composition and a metal ion battery including the same. According to an embodiment of the present disclosure, the electrolyte composition of the present disclosure not only includes the metal salt and the ionic liquid, but also includes an additive with a specific structure. The addition of additives can make the electric field on the surface of the metal electrode (such as the aluminum electrode of the aluminum ion battery) uniform during the charging and discharging cycle of the battery (such as the aluminum ion battery), thereby improving the uniformity of the deposition of the metal electrode and helping to inhibit the The formation of dendrites on the surface of the metal electrode also improves the self-corrosion effect of the surface of the aluminum electrode. answer. In this way, the performance of the battery can be effectively improved and the cycle life of the battery can be prolonged.

According to an embodiment of the present disclosure, the electrolyte composition of the present disclosure includes a metal salt having the structure represented by formula (I), an ionic liquid, and an additive,

M _i X _j formula (I) wherein M is lithium ion, sodium ion, potassium ion, beryllium ion, magnesium ion, calcium ion, scandium ion, yttrium ion, titanium ion, zirconium ion, hafnium ion, vanadium ion, niobium ion , tantalum ion, chromium ion, molybdenum ion, tungsten ion, manganese ion, onium ion, rhenium ion, iron ion, ruthenium ion, osmium ion, cobalt ion, rhodium ion, iridium ion, nickel ion, palladium ion, platinum ion, copper ion ion, silver ion, gold ion, zinc ion, cadmium ion, mercury ion, indium ion, thallium ion, tin ion, lead ion, arsenic ion, antimony ion, bismuth ion, gallium ion, or aluminum ion; X series F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , CF ₃ SO ₃ ^- , NO ₃ ^- , CH ₃ CO ₂ ^- , SO ₄ ^2- , C ₂ O ₄ ²⁻ , [B(C ₂ O ₄ ) ₂ ] ⁻ ; and, i is 1, 2, 3, 4, 5, or 6. The molar ratio of the metal salt to the ionic liquid may be greater than or equal to 1.0, for example, 1.0 to 2.05, and for example, 1.1 to 2.0.

For example, the aforementioned metal salt can be LiCl, LiBF ₄ , LiPF ₆ , LiNO ₃ , LiCH ₃ CO ₂ , Li[B(C ₂ O ₄ ) ₂ ], NaCl, NaBF ₄ , NaPF ₆ , Na ₂ SO ₄ , Na ₂ C ₂ O ₄ , KCl, BeCl ₂ , MgCl ₂ , CaCl ₂ , ScCl ₃ , YCl ₃ , TiCl ₂ , TiCl ₃ , TiCl ₄ , ZrCl ₄ , HfCl ₄ , VCl ₂ , VCl ₃ , VCl ₄ , VCl ₅ , NbCl ₅ , TaCl ₅ , CrCl ₂ , CrCl ₃ , MoCl ₃ , MoCl ₅ , WCl ₅ , WCl ₆ , MnCl ₂ , TcCl ₄ , ReCl ₃ , FeCl ₂ , FeCl ₃ , RuCl ₃ , OsCl ₄ , CoCl ₂ , RhCl ₃ , IrCl ₄ , NiCl ₂ , NiSO ₄ , PdCl ₂ , PtCl ₂ , PtCl ₄ , CuCl, CuCl ₂ , CuSO ₄ , AgCl , AuCl ₃ , ZnCl ₂ , ZnCl ₄ , CdCl ₂ , HgCl ₂ , Hg ₂ Cl ₂ , InCl ₃ , TlCl, SnCl ₄ , PbCl ₄ , AsCl ₃ , SbCl ₃ , SbCl ₅ , BiCl ₃ , GaCl ₃ , AlF ₂ , AlF ₃ , AlCl ₂ , AlCl ₃ , AlBr ₂ , AlBr ₃ , AlI ₂ , AlI ₃ , Al(BF ₄ ) ₂ , Al(BF ₄ ) ₃ , Al(PF ₆ ) ₂ , Al(PF ₆ ) ₃ , Al[(CF ₃ SO ₂ ) ₂ N] ₂ , Al[(CF ₃ SO ₂ ) ₂ N] ₃ , Al(CF ₃ SO ₃ ) ₂ , Al(CF ₃ SO ₃ ) ₃ , or a combination thereof. In some embodiments, the aforementioned metal salt may be AlCl ₃ .

According to an embodiment of the present disclosure, the aforementioned ionic liquid may have a structure represented by formula (II):

[A] _k [B] _l formula (II) wherein, A can be imidazolium cation (imidazolium cation), pyrrolium cation (pyrrolium cation), pyrrolidinium cation (pyrrolidinium cation), pyrrolidinium cation (pyrrolidinium cation) , pyridinium cation, ammonium cation, indazolium cation, pyrimidinium cation, azaannulenium cation, azathiazolium cation ( azathiazolium cation), benzimidazolium cation, benzofuranium cation, benzotriazolium cation, borolium cation, choline cation (cholinium cation), cinnolinium cation, diazabicyclodecenium cation, diazabicyclononenium cation, diazabicycloundeca Diazabicyclo-undecenium cation, dithiazolium cation, furanium cation, guanidinium cation, indolinium cation, indolinium cation (indolium cation), morpholinium cation, oxaborolium cation, oxaphospholium cation, oxazinium cation, oxa oxazolium cation, isoxazolium cation, iso-oxazolium cation, oxathiazolium cation, pentazolium cation, phospholium cation, Phosphonium cation (phos phonium cation), phthalazinium cation, piperazinium cation, piperidinium cation, pyranium cation, pyrazinium cation, pyrazinium cation pyrazolium cation, pyridazinium cation, quinazolinium cation, quinolinium cation, iso-quinolinium cation, quinoxa quinoxalinium cation, selenozolium cation, sulfonium cation, tetrazolium cation, iso-thiadiazolium cation, thiazinium cation thiazinium cation, thiazolium cation, thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation ), triazolium cation (triazolium cation), iso-triazolium cation (iso-triazolium cation), or uronium cation (uronium cation); B can be F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , CF ₃ SO ₃ ^- , NO ₃ ^- , CH ₃ CO ₂ ^- , SO ₄ ^2- , C ₂ O ₄ ^2- , or [B(C ₂ O ₄ ) ₂ ] ⁻ ; and, k is 1, 2, 3, 4, 5, or 6; l is 1, 2, 3, 4, 5, or 6.

For example, the aforementioned ionic liquid can be imidazolium chloride (eg: alkylimidazolium chloride), pyrrolium chloride (eg: alkylpyrrolium chloride) (alkylpyrrolium chloride), pyrrolinium chloride (eg: alkylpyrrolinium chloride), pyrrolidinium chloride (eg: alkylpyrrolidinium chloride) (alkylpyrrolidinium chloride), pyridinium chloride (eg: alkylpyridinium chloride), ammonium chloride (eg: alkylammonium chloride), Indazolium chloride (eg: alkylindazolium chloride), pyrimidinium chloride (eg: alkylpyrimidinium chloride), aza azaannulenium chloride (eg: alkylazaannulenium chloride), azathiazolium chloride (eg: alkylazathiazolium chloride) chloride), benzimidazolium chloride (eg: alkylbenzimidazolium chloride), benzofuranium chloride (eg: alkylbenzimidazolium chloride) (alkylbenzofuranium chloride), benzotriazolium chloride (for example: alkylbenzotriazolium chloride), borolium chloride (for example: Alkylborolium chloride (alkylborolium chloride), choline chloride (choli) nium chloride (eg: alkylcholine chloride), cinnolinium chloride (eg: alkylcinnolinium chloride), diazabicyclodecene Diazabicyclodecenium chloride (eg: alkyldiazabicyclodecenium chloride), diazabicyclononenium chloride (eg: alkyldiazabicyclononenium chloride) Alkyldiazabicyclononenium chloride), diazabicyclo-undecenium chloride (eg: alkyldiazabicyclo-undecenium chloride) -undecenium chloride), dithiazolium chloride (eg: alkyldithiazolium chloride), furanium chloride (eg: alkylfuranium chloride) chloride), guanidinium chloride (eg: alkylguanidinium chloride), indolinium chloride (eg: alkyl indolinium chloride) (alkylindolinium chloride), indolium chloride (eg: alkylindolium chloride), morpholinium chloride (eg: alkyl morpholinium chloride) (alkylmorpholinium chloride), oxaborolium chloride (for example: alkyloxaborolium chloride), oxaphospholium chloride chloride) (for example: alkyloxaphospholium chloride), oxazinium chloride (for example: alkyloxaphospholium chloride) alkyloxazinium chloride), oxazolium chloride (eg: alkyloxazolium chloride), iso-oxazolium chloride (eg: alkyliso oxazolium chloride (alkyliso-oxazolium chloride), oxathiazolium chloride (for example: alkyloxathiazolium chloride), pentazolium chloride (for example: alkylpentazolium chloride), phospholium chloride (eg: alkylphospholium chloride), phosphonium chloride chloride (eg: alkylphosphonium chloride), phthalazinium chloride (eg: alkylphthalazinium chloride), piperazinium chloride ) (for example: alkylpiperazinium chloride), piperidinium chloride (for example: alkylpiperidinium chloride), pyranium chloride ) (eg: alkylpyranium chloride), pyrazinium chloride (eg: alkylpyrazinium chloride), pyrazolium chloride ) (eg: alkylpyrazolium chloride), pyridazinium chloride (eg: alkylpyridazinium chloride), quinazolinium chloride chloride) (eg: alkylquinazolinium chloride), quinoliniu chloride m chloride) (for example: alkylquinolinium chloride), iso-quinolinium chloride (for example: alkyliso-quinolinium chloride), quinoline quinoxalinium chloride (eg: alkylquinoxalinium chloride), selenozolium chloride (eg: alkylselenozolium chloride) , sulfonium chloride (eg: alkylsulfonium chloride), tetrazolium chloride (eg: alkyltetrazolium chloride), iso iso-thiadiazolium chloride (eg: alkyliso-thiadiazolium chloride), thiazinium chloride (eg: alkyl thiadiazolium chloride) salt (alkylthiazinium chloride), thiazolium chloride (eg: alkylthiazolium chloride), thiophenium chloride (eg: alkylthiophenium chloride) )), thiuronium chloride (eg: alkylthiuronium chloride), triazadecenium chloride (eg: alkyl triazadecenium) alkyltriazadecenium chloride), triazinium chloride (eg: alkyltriazinium chloride), triazolium chloride (eg: alkyltriazole) Onium chloride (alkyltriazolium chloride), iso-triazolium chloride (iso-triazolium chloride) (for example: alkyl isotriazolium chloride (alkyltriazolium chloride) iso-triazolium chloride), or uronium chloride (eg: alkyluronium chloride). In some embodiments, the aforementioned ionic liquid can be 1-ethyl-3-methylimidazolium chloride (1-ethyl-3-methylimidazolium chloride, [EMI ⁺ ][Cl ^- ]), 1-butyl- 3-methylimidazolium chloride (1-butyl-3-methylimidazolium chloride, [BMI ⁺ ][Cl ^- ]), or a combination thereof.

According to an embodiment of the present disclosure, the aforementioned additives may include substituted or unsubstituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compounds with higher polarity. Wherein, the unsubstituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compound can be, for example, pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole ), benzimdazole, pyridine, indole, indoline, carbazole, pyridazine, pyrimidine, pyrazine, Purine, acridine, phenazine, phenothiazine, quinolone, iso-quinolone, pteridine, 1,10-phenanthrene 1,10-phenanthroline, 1,7-phenanthroline, 4,7-phenanthroline, 1,10-phenanthroline monohydrate (1,10-phenanthroline monohydrate), or 1,10-phenanthroline hydrochloride monohydrate (1,10-phenanthroline monohydrochloride monohydrate).

、

，其中R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、 R⁸、R⁹、及R¹⁰係各自獨立為氫或C_1-10烷基。 The substituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compound refers to the C ₅ -C ₃₀ nitrogen-containing heterocyclic compound whose hydrogen on at least one carbon atom is substituted by R, wherein R can be halogen, cyano, C _{1 -10} alkyl, C _1-10 alkoxy, C _1-5 aminoalkyl, -NR ¹ R ² ,

,

, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently hydrogen or C _1-10 alkyl.

When the aforementioned R is a C _1-10 alkyl group, it can be a linear or branched chain alkyl group, for example, can be methyl (methyl), ethyl (ethyl), propyl (propyl) ), butyl (butyl), pentyl (pentyl), hexyl (hexyl), heptyl (heptyl), octyl (octyl), nonyl (nonyl), decyl (decyl), or its isomer (isomer) ). When the aforementioned R is a C _1-10 alkoxy group, it can be a linear or branched chain alkoxy group. For example, C _1-10 alkoxy may be methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy Hexoxy, heptoxy, octoxy, nonoxy, decoxy, or isomers thereof. When the aforementioned R is a C _1-5 aminoalkyl group, it can be a linear or branched chain aminoalkyl group, for example, a C _1-5 aminoalkyl group can be an aminomethyl group (aminomethyl, structural formula NH ₂ CH ₂ -), aminoethyl (aminoethyl, structural formula NH ₂ C ₂ H ₄ -), aminopropyl (aminopropyl, structural formula NH ₂ C ₃ H ₆ -), or its isomers.

When the aforementioned R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ is a C _1-10 alkyl group, it may be straight or branched. The alkyl group of the branched chain, for example, can be methyl (methyl), ethyl (ethyl), propyl (propyl), butyl (butyl), pentyl (pentyl), hexyl (hexyl), heptyl (heptyl), octyl (octyl), nonyl (nonyl), decyl (decyl), or an isomer thereof.

For example, the aforementioned substituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compound can be 3,4,7,8-tetramethyl-1,10-phenanthroline (3,4,7,8-tetramethyl-1 , 10-phenanthroline), 4,7-dihydroxy-1,10-phenanthroline (4,7-dihydroxy-1,10-phenanthroline), 5,6-dimethyl-1,10-phenanthroline ( 5,6-dimethyl-1,10-phenanthroline), 5-chloro-1,10-phenanthroline (5-chloro-1,10-phenanthroline), 1,10-phenanthroline-5,6-dione (1,10-phenanthroline-5,6-dione), 4-pyridinecarboxylic acid hydrazide, 3-pyridinecarboxylic acid hydrazide, 4-pyridinecarboxylic acid hydrazide (4-pyridinecarboxylic acid hydrazide) pyridyl hydrazide), 4-pyridinecarboxaldehyde, 4-methoxypyridine, 3-methoxypyridine, 2-methoxypyridine, 4-aminopyridine (4-aminopyridine), 4-(aminomethyl)pyridine (4-(aminomethyl)pyridine), 4-carboxamide (pyridine-4-carboxamide), 3-carboxamide (pyridine-3-carboxamide) ), pyridine-2-carboxamide, pyridine-3-carboxylic acid, or Janus Green B (8-(4-Dimethylaminophenyl)diazenyl-N , N-diethyl-10-phenylphenazin-10-ium-2-amine chloride).

According to an embodiment of the present disclosure, the aforementioned additives may include pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole, benzimdazole ), pyridine, indole, indoline, carbazole, pyridazine, pyrimidine, pyrazine (pyrazine), purine (purine), acridine (acridine), phenazine (phenazine), phenothiazine (phenothiazine), quinolone (quinolone), isoquinolone (iso-quinolone), pteridine (pteridine), 1 ,10-phenanthroline (1,10-phenanthroline), 1,7-phenanthroline (1,7-phenanthroline), 4,7-phenanthroline (4,7-phenanthroline), 1,10-phenanthroline 1,10-phenanthroline monohydrate, 1,10-phenanthroline monohydrochloride monohydrate, 3,4,7,8-tetramethyl-1, 10-phenanthroline (3,4,7,8-tetramethyl-1,10-phenanthroline), 4,7-dihydroxy-1,10-phenanthroline (4,7-dihydroxy-1,10-phenanthroline) , 5,6-dimethyl-1,10-phenanthroline (5,6-dimethyl-1,10-phenanthroline), 5-chloro-1,10-phenanthroline (5-chloro-1,10-phenanthroline) phenanthroline), 1,10-phenanthroline-5,6-dione (1,10-phenanthroline-5,6-dione), 4-pyridinecarboxylic acid hydrazide, 3-pyridinecarboxylic acid Hydrazine (3-pyridinecarboxylic acid hydrazide), 4-pyridyl hydrazide (4-pyridyl hydrazide), 4-pyridinecarboxaldehyde (4-pyridinecarboxaldehyde), 4-methoxypyridine (4-methoxypyridine), 3-methoxypyridine ( 3-methoxypyridine), 2-methoxypyridine (2-methoxypyridine), 4-aminopyridine (4-aminopyridine), 4-methylaminopyridine (4-(aminomethyl)pyridine), 4-methylaminopyridine (pyridine- 4-carboxamide), 3-carboxamide (pyridine-3-carboxamide), 2-carboxamide (pyridine-2-carboxamide), pyridine-3-carboxylic acid (pyridine-3-carboxylic acid), Janus Green B (Janus Green B, 8-(4-Dimethylaminophenyl)diazenyl-N,N-diethyl-10-phenylphenazin- 10-ium-2-amine chloride), or a combination of the above.

According to some embodiments of the present disclosure, the aforementioned additives may include 1,10-phenanthroline, 1,7-phenanthroline, 4,7-phenanthroline ( 4,7-phenanthroline), 5-chloro-1,10-phenanthroline (5-chloro-1,10-phenanthroline), 4-pyridinecarboxylic acid hydrazide, Jianna green B (Janus Green B, 8-(4-Dimethylaminophenyl)diazenyl-N,N-diethyl-10-phenylphenazin-10-ium-2-amine chloride), pyridine-3-carboxylic acid, or a combination of the above .

According to an embodiment of the present disclosure, in the electrolyte composition of the present disclosure, the molar ratio of the metal salt to the ionic liquid may be greater than or equal to 1.0, such as 1.0 to 2.05, or 1.1 to 2.0. For example, the molar ratio of the metal salt to the ionic liquid can be about 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In addition, according to an embodiment of the present disclosure, based on the total weight of the metal salt and the ionic liquid, the content of the additive may be 0.05 wt % to 20 wt %. If the content of the additive is too low, it is equivalent to the case of no addition, and the surface of the metal electrode is prone to dendrites and self-corrosion. If the content of the additive is too high, the additive may be poorly soluble in the mixture of the metal salt and the ionic liquid (ie, the resulting electrolyte composition is cloudy and precipitates), making the electrolytic The conductivity of the solution decreases, resulting in a decrease in capacitance. In another embodiment, the content of the additive may be 0.05 wt % to 15 wt %. In yet another embodiment, the content of the additive may be 0.05wt% to 10wt%.

According to an embodiment of the present disclosure, the electrolyte composition of the present disclosure can optionally further include a solvent, which can be used to dilute and adjust the viscosity of the composition, so that the composition can be easily injected between the positive electrode and the negative electrode when the battery is packaged, and it is beneficial to in ion transport. The solvent can be furan, carbonate, ester, ether, benzene, nitrile, selenium, ketone solvent, for example, such as tetrahydrofuran (THF), dimethyl ether (dimethyl ether), Ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, trimethyl phosphate phosphate), dimethoxyethane, toluene, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, or the above combination.

According to an embodiment of the present disclosure, the present disclosure also provides a metal ion battery. Please refer to FIG. 1 , which is a schematic diagram of a metal-ion battery 100 according to an embodiment of the present disclosure. The metal ion battery 100 can include a positive electrode 10 , a negative electrode 12 , and a separator 14 , wherein the separator 14 can be disposed between the positive electrode 10 and the negative electrode 12 , so that the negative electrode is connected to the positive electrode with the separator 14 . spaced apart to avoid direct contact between the positive electrode 10 and the negative electrode 12 . The metal ion battery 100 includes the above-mentioned electrolyte composition 20 disposed in the metal ion battery 100 between the positive electrode and the negative electrode, so that the electrolyte composition 20 is in contact with the positive electrode 10 and the negative electrode 12 . The metal-ion battery 100 can be a rechargeable secondary battery, but the present disclosure also covers primary batteries.

According to an embodiment of the present disclosure, the positive electrode 10 may include a positive electrode collector layer and a positive electrode active material disposed on the positive electrode collector layer. According to an embodiment of the present disclosure, the positive electrode 10 can also be composed of the positive electrode current collecting layer and the positive electrode active material. According to an embodiment of the present disclosure, the positive electrode collector layer may include a conductive carbon substrate, a metal material, a metal material with a porous structure, or a combination thereof. The metal material can be, for example, aluminum, nickel, copper, and molybdenum. The conductive carbon substrate is, for example, carbon cloth, carbon felt, or carbon paper. For example, the conductive carbon substrate may have a sheet resistance of about 1 mΩ. cm ² to 6mΩ. cm ² , and the carbon content is greater than about 65 wt%. According to an embodiment of the present disclosure, the above-mentioned metal material with a porous structure, such as a 3D mesh structure metal material (such as nickel mesh, copper mesh, or molybdenum mesh) or a foamed structure metal material (such as foamed nickel, foamed copper, or foamed molybdenum). According to an embodiment of the present disclosure, the metal material having a porous structure may have a porosity P of about 10% to 99.9% (for example, about 60% or 70%). The porosity P may be determined by the following formula: P=V1/ V2×100%, in which the volume occupied by the pores in the V1 series positive electrode collector layer, and the total volume of the V2 series positive electrode collector layer. According to an embodiment of the present disclosure, the collector layer may be a composite layer of a conductive carbon substrate and a metal material.

According to an embodiment of the present disclosure, the positive electrode active material may be a carbon material with a layered structure, a layered double hydroxide, a layered oxide, a layered chalcogenide, or a vanadium oxide. compounds, or metal sulfides, agglomerates of the above materials, or a combination of the above. According to an embodiment of the present disclosure, the layered carbon material may be graphite, carbon nanotubes, graphene, or a combination thereof. According to an embodiment of the present disclosure, the layered carbon material may be an intercalated carbon material, such as graphite (including natural graphite, artificial graphite, pyrolytic graphite, foamed graphite, flakes) graphite, or expanded graphite), graphene, carbon nanotubes, or a combination of the above materials. According to an embodiment of the present disclosure, the positive electrode active material can be grown directly (eg, chemical vapor deposition (CVD) is used to form the positive electrode active material) on the positive electrode current collector layer (ie, there is no medium between the two). ), or use adhesives (such as: polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethyl cellulose, polyvinylidene fluoride, polystyrene butadiene copolymer, fluorinated rubber, polyurethane, polyethylene pyrrolidone, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polybutadiene, polyacrylic acid, or a combination thereof) to fix the positive electrode active material on the positive electrode collector layer. According to an embodiment of the present disclosure, when the positive electrode current collecting layer is a metal material with a porous structure, the positive electrode active material can be further filled into the pores of the metal material.

According to the embodiment of the present disclosure, the material of the isolation film 14 can be glass fiber, polyethylene (PE), polypropylene (Polypropylene, PP), non-woven fabric, wood fiber, poly (ether sulfones), PES ), ceramic fibers, or a combination of the above.

According to the disclosed embodiment, the negative electrode 12 includes a negative electrode active material, wherein the negative electrode active material may include a metal or an alloy of the metal, a carbon material with a layered structure, a layered double hydroxide, Layered oxides, layered chalcogenides, vanadium oxides, metal sulfides, agglomerates of the above, or a combination of the above. According to an embodiment of the present disclosure, the metal may be sodium, potassium, beryllium, magnesium, calcium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, onium, rhenium, iron, Ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, indium, thallium, tin, lead, antimony, bismuth, gallium, or aluminum. According to an embodiment of the present disclosure, the layered carbon material may be graphite, carbon nanotubes, graphene, or a combination thereof. According to an embodiment of the present disclosure, the layered carbon material may be an intercalated carbon material, such as graphite (including natural graphite, artificial graphite, pyrolytic graphite, foamed graphite, flake graphite, or expanded graphite), graphene , carbon nanotubes or a combination of the above materials. According to an embodiment of the present disclosure, the negative electrode 12 may further include a negative electrode current collector layer, and the negative electrode active material can be directly grown (eg, by chemical vapor deposition to form the positive electrode active material) on the negative electrode current collector layer (ie both without any medium in between), or use adhesives (such as: polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethyl cellulose, polyvinylidene fluoride, polystyrene butadiene copolymer, fluorine rubber, poly urethane, polyvinylpyrrolidone, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polybutadiene, polyacrylic acid, or a combination of the above) fix the negative electrode active material on the negative electrode current collecting layer. According to an embodiment of the present disclosure, the negative electrode collector layer may include a conductive carbon substrate, such as carbon cloth, carbon felt, or carbon paper. For example, the conductive carbon substrate may have a sheet resistance of about 1 mΩ. cm ² to 6mΩ. cm ² , and the carbon content is greater than about 65 wt%. According to an embodiment of the present disclosure, the negative electrode collector layer may include a metal foil or a metal material with a porous structure, such as a metal material with a 3D mesh structure (such as a nickel mesh, a copper mesh, or a molybdenum mesh) or a metal material with a foam structure (such as: foamed nickel, foamed copper, or foamed molybdenum). In some embodiments, the negative electrode collector layer may include lithium mesh, lithium foil, lithium foam, sodium mesh, sodium foil, foamed sodium, potassium mesh, potassium foil, potassium foam, beryllium mesh, beryllium foil, foamed Beryllium, magnesium mesh, magnesium foil, magnesium foam, calcium mesh, calcium foil, calcium foam, scandium mesh, scandium foil, scandium foam, yttrium mesh, yttrium foil, foamed yttrium, titanium mesh, titanium foil, foam Titanium, zirconium mesh, zirconium foil, foamed zirconium, hafnium mesh, hafnium foil, foamed hafnium, vanadium mesh, vanadium foil, foamed vanadium, niobium mesh, niobium foil, foamed niobium, tantalum mesh, tantalum foil, foamed Tantalum, chrome mesh, chrome foil, foamed chrome, molybdenum mesh, molybdenum foil, foamed molybdenum, tungsten mesh, tungsten foil, foamed tungsten, manganese mesh, manganese foil, foamed manganese, tungsten mesh, tungsten foil, foam Onium, rhenium mesh, rhenium foil, foamed rhenium, iron mesh, iron foil, foamed iron, ruthenium mesh, ruthenium foil, foamed ruthenium, osmium mesh, osmium foil, foamed osmium, cobalt mesh, cobalt foil, foam cobalt, rhodium mesh, rhodium foil, rhodium foam, iridium mesh, iridium foil, foam iridium, nickel mesh, nickel foil, foam nickel, palladium mesh, palladium foil, palladium foam, platinum mesh, platinum foil, foam Platinum, copper mesh, copper foil, foamed copper, silver mesh, silver foil, foamed silver, gold mesh, gold foil, foamed gold, zinc mesh, zinc foil, foamed zinc, cadmium mesh, cadmium foil, foamed cadmium, indium Mesh, indium foil, foamed indium, thallium mesh, thallium foil, foamed thallium, tin mesh, tin foil, foamed tin, lead mesh, lead foil, foamed lead, antimony mesh, antimony foil, foamed antimony, bismuth mesh , bismuth foil, foamed bismuth, gallium mesh, gallium foil, foamed gallium, aluminum mesh, aluminum foil, foamed aluminum, titanium nitride, conductive polymer, or a combination of the above. According to an embodiment of the present disclosure, the metal material having a porous structure may have a porosity P of about 50% to 80% (eg, about 60% or 70%). The porosity P may be determined by the following formula: P=V1/ V2×100%, in which the volume occupied by the pores in the V1 series negative electrode current collector layer, and the total volume of the V2 series negative electrode current collector layer. According to an embodiment of the present disclosure, the negative electrode collector layer may be a composite layer of a conductive carbon substrate and a metal material. According to an embodiment of the present disclosure, when the negative electrode current collecting layer is a metal material with a porous structure, the negative electrode active material can be further filled into the pores of the metal material. According to an embodiment of the present disclosure, the negative electrode can also be composed of the negative electrode current collecting layer and the negative electrode active material. According to the disclosed embodiment, the materials and structures of the positive electrode 10 and the negative electrode 12 are the same.

In order to make the above-mentioned and other objects, features, and advantages of the present disclosure more obvious and easy to understand, the following specific embodiments are given in conjunction with the accompanying drawings, and are described in detail as follows:

Preparation of Electrolyte Composition

Preparation of Comparative Example 1

Take aluminum chloride (AlCl ₃ ) and 1-butyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium chloride, [BMI ⁺ ][Cl ^- ]) ionic liquid mixed (AlCl ₃ and [BMI] The molar ratio of ⁺ ][Cl ^- ] is 1.5:1), and since the two have room temperature eutectic properties, they can be converted from solid phase to liquid phase. After the mixed solution was continuously stirred for about 12 hours, an electrolyte composition (1) was obtained. The obtained solution of electrolyte composition (1) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation of Comparative Example 2

First, take aluminum chloride (AlCl ₃ ) and 1-butyl-3-methylimidazolium chloride ([BMI ⁺ ][Cl ^- ]) ionic liquid mixed (AlCl ₃ and [BMI ⁺ ][Cl ^- ] The molar ratio is 1.5:1). Next, based on the total weight of AlCl ₃ and [BMI ⁺ ][Cl ^- ], 0.38wt% of Naphthalene (purchased from Aldrich, product number 184500) (code: NAP) was added, and the stirring was continued for about 12 hours. , the electrolyte composition (2) was obtained. The obtained solution of electrolyte composition (2) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 1

First, take aluminum chloride (AlCl ₃ ) and 1-butyl-3-methylimidazolium chloride ([BMI ⁺ ][Cl ^- ]) ionic liquid mixed (AlCl ₃ and [BMI ⁺ ][Cl ^- ] The molar ratio is 1.5:1). Next, based on the total weight of AlCl ₃ and [BMI ⁺ ][Cl ^- ], 0.38wt% of 1,10-phenanthroline (purchased from Alfa Aesar, product number A13163) was added ( Code: 110PH), and after continuous stirring for about 12 hours, the electrolyte composition (3) was obtained. The obtained solution of electrolyte composition (3) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 2

The preparation method of electrolyte composition (3) described in Preparation Example 1 was carried out, except that the additive was changed from 1,10-phenanthroline to 1,7-phenanthroline (purchased from Alfa Aesar, product number 30909) (code: 17PH), to obtain the composition of the electrolyte thing (4). The obtained solution of electrolyte composition (4) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 3

The preparation method of electrolyte composition (3) described in Preparation Example 1 was carried out, except that the additive was changed from 1,10-phenanthroline to 5-chloro-1,10-phenanthroline (5-chloro-1, 10-phenanthroline) (purchased from Alfa Aesar, product number 31180) (code: 110PH5C1) to obtain electrolyte composition (5). The obtained solution of electrolyte composition (5) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 4

Carry out the preparation method of the electrolyte composition (3) described in Preparation Example 1, except that the additive is changed from 1,10-phenanthroline to Kena Green B(8-(4-Dim ethylaminophenyl)diazenyl-N,N -diethyl-10-phenylphenazin-10-ium-2-amine chloride) (purchased from Acros, product number 191680250) (code: JB) to obtain electrolyte composition (6). The obtained electrolyte composition (6) solution was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 5

The preparation method of electrolyte composition (3) described in Preparation Example 1 was carried out, except that the additive was changed from 1,10-phenanthroline to pyridine-3-carboxylic acid (purchased from Sigma- Aldrich, product number N4126) (code: NA), to obtain electrolyte composition (7). The obtained solution of electrolyte composition (7) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 6

The preparation method of electrolyte composition (3) described in Preparation Example 1 was carried out, except that the additive was changed from 1,10-phenanthroline to 4-pyridinecarboxylic acid hydrazide (purchased from Alfa Aesar). , product number A10583) (code: INH) to obtain electrolyte composition (8). The obtained solution of electrolyte composition (8) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 7

The preparation method of the electrolyte composition (8) described in Preparation Example 6 was carried out, except that the amount of 4-pyridinecarboxylate hydrazine was reduced from 0.38 wt % to 0.05 wt % to obtain an electrolyte composition (9). The obtained solution of electrolyte composition (9) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 8

The preparation method of the electrolyte composition (3) described in Preparation Example 1 was carried out, except that the additives and their amounts were changed from 1,10-phenanthroline (0.38wt%) to 4-pyridinecarboxyhydrazine and pyridine-3carboxylate. acid (0.05 wt % and 0.05 wt %, respectively) to obtain electrolyte composition (10). The obtained solution of electrolyte composition (10) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 9

The preparation method of the electrolyte composition (12) described in Preparation Example 10 was carried out, except that the amounts of the additives 4-pyridinecarboxylic acid hydrazine and pyridine-3carboxylic acid were increased from 0.05wt% and 0.05wt% to 0.38wt% and 0.38wt% wt% to obtain an electrolyte composition (11). The obtained solution of electrolyte composition (11) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 10

First, take aluminum chloride (AlCl ₃ ) and 1-butyl-3-methylimidazolium chloride ([BMI ⁺ ][Cl ^- ]) ionic liquid mixed (AlCl ₃ and [BMI ⁺ ][Cl ^- ] The molar ratio is 1.5:1). Next, based on the total weight of AlCl ₃ and [BMI ⁺ ][Cl ^- ], 0.38wt% of the additive 4-pyridinecarboxylic acid hydrazine and 1wt% of the solvent tetrahydrofuran (THF) were added, and the stirring was continued for about 12 hours. After that, an electrolyte composition (12) was obtained.

Preparation Example 11

The preparation method of the electrolyte composition (12) described in Preparation Example 10 was carried out, except that the amount of the solvent tetrahydrofuran was increased from 1 wt% to 5 wt% to obtain the electrolyte composition (13).

Preparation of Comparative Example 3

Take aluminum chloride (AlCl ₃ ) and 1-ethyl-3-methylimidazolium chloride ([EMI ⁺ ][Cl ^- ]) ionic liquid mixed (AlCl ₃ and [EMI ⁺ ][Cl ^- ] Molar The ratio is 2:1), because the two have room temperature eutectic properties, so they can be converted from solid phase to liquid phase. After the mixed solution was continuously stirred for about 12 hours, an electrolyte composition (14) was obtained. The obtained solution of the electrolyte composition (14) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 12

First, take aluminum chloride (AlCl ₃ ) and 1-ethyl-3-methylimidazolium chloride ([EMI ⁺ ][Cl ^- ]) ionic liquid mixed (AlCl ₃ and [EMI ⁺ ][Cl ^- ] The molar ratio is 2:1). Next, based on the total weight of AlCl ₃ and [EMI ⁺ ][Cl ^- ], 0.38wt% of pyridine-3-carboxylic acid (purchased from Sigma-Aldrich, product number N4126) ( Code: NA), and after continuous stirring for about 12 hours, an electrolyte composition (15) was obtained. The obtained solution of electrolyte composition (15) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 13

The preparation method of the electrolyte composition (15) described in Preparation Example 12 was carried out, except that the amount of pyridine-3-carboxylic acid was increased from 0.38 wt% to 10 wt% to obtain an electrolyte composition (16). The obtained solution of electrolyte composition (16) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 14

The preparation method of the electrolyte composition (15) described in Preparation Example 12 was carried out, except that the additive and its amount were changed from pyridine-3-carboxylic acid 0.38wt% to Gena Green B (8-(4-Dimethylaminophenyl)diazenyl-N , N-diethyl-10-phenylphenazin-10-ium-2-amine chloride) 10wt% to obtain an electrolyte composition (17). The obtained solution of electrolyte composition (17) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 15

The preparation method of the electrolyte composition (17) described in Preparation Example 14 was carried out, except that the amount of Kena Green B was increased from 10wt% to 15wt% to obtain the electrolyte composition (18). The obtained solution of electrolyte composition (18) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 16

The preparation method of the electrolyte composition (17) described in Preparation Example 14 was carried out, except that the amount of Kena Green B was increased from 10 wt % to 20 wt % to obtain the electrolyte composition (19). The obtained solution of electrolyte composition (19) was in a clear state with good fluidity, and showed a good eutectic state.

Preparation Example 17

The preparation method of the electrolyte composition (17) described in Preparation Example 14 was carried out, except that the amount of Kena Green B was increased from 10 wt% to 25 wt% to obtain the electrolyte composition (20). Although the fluidity of the obtained electrolyte composition (20) solution was good, the solution state was turbid and precipitation occurred, and the eutectic state was not good, so it could not be used.

metal ion battery

Comparative Example 1

First, provide an aluminum foil with a thickness of 0.025mm (purchased from Alfa Aesar), cut it to obtain a negative electrode (size 20mm×20mm), and provide a nickel foam plate (size 100 mm×100 mm, thickness 0.2 mm, porosity 90%, and pore diameter 200 μm). Next, the nickel foamed plate is placed in a vacuum high-temperature furnace, and hydrogen and argon gas (as a transport gas) are introduced into it, and methane is simultaneously introduced to carry out graphite vapor deposition (the temperature is between 900 and 1100 ° C) to obtain A nickel foamed plate with a graphite layer coating on the surface (with a graphite loading of 800-1500 mg) was cut to a size of 20 mm×20 mm to obtain a positive electrode (graphite electrode). Then, a separator (glass filter paper, product number Whatman GF/C) was provided. Next, the negative electrode, the separator, and the positive electrode are arranged in the order, encapsulated with an aluminum plastic film, and injected into the electrolyte composition (1) to obtain a metal ion battery (1).

Next, use the charge-discharger (BST408-5V-10A) of Newwell Electronics to conduct a charge-discharge cycle test (charged to 2.3v) on the metal-ion battery (1) at a current of 500mA/g, and measure the metal-ion battery ( 1) The Coulomb efficiency, the capacity retention rate at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is less than 80% are shown in Table 1.

Comparative Example 2

The method for preparing the metal ion battery (1) in Comparative Example 1 was carried out, except that the electrolyte composition (2) was used instead of the electrolyte composition (1) to obtain a metal ion battery (2).

Next, the coulombic efficiency of the metal-ion battery (2), the capacity retention rate at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is lower than 80% were measured in the above-mentioned manner. The results are shown in Table 1.

Examples 1-9

The preparation method of the metal ion battery (1) in Comparative Example 1 was carried out, except that the electrolyte composition (3)-(11) was replaced by the electrolyte composition (1), respectively, to obtain the metal ion battery (3)-(11).

Next, the Coulombic efficiencies of the metal-ion batteries (3)-(11), the capacity retention rates at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is lower than 80% were measured respectively, and the results are shown in the table below. 1 shown.

Table 1

It can be seen from Table 1 that, compared with Comparative Example 1 and Comparative Example 2, the Coulombic efficiencies of Examples 1 to 11 are improved. It is obvious that adding nitrogen-containing heterocyclic compound additives to the electrolyte composition can effectively improve the dissolution/dissolution of metal electrodes. The uniformity of deposition, and improve battery performance and prolong battery cycle life.

Example 10

The preparation method of the metal ion battery (1) described in Comparative Example 1 was carried out, except that the electrolyte composition (12) was replaced by the electrolyte composition (1) to obtain a metal ion battery (12).

Next, the coulombic efficiency of the metal-ion battery (12), the capacity retention rate at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is lower than 80% are respectively measured in the above-mentioned manner. The measurement result: the Coulomb efficiency is: 99.6%, 77.6% and 55.5% of the capacity retention rate of the 2000th cycle and 3000th cycle, and 1887 cycles in which the discharge capacity is lower than 80%.

Example 11

The preparation method of the metal ion battery (1) described in Comparative Example 1 was carried out, except that the electrolyte composition (13) was replaced by the electrolyte composition (1) to obtain a metal ion battery (13).

Next, the coulombic efficiency of the metal-ion battery (13), the capacity retention rate at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is lower than 80% are respectively measured in the above-mentioned manner. The measurement result: the Coulomb efficiency is: 99.2%, 77.8% and 56.5% of the capacity retention rate of the 2000th cycle and 3000th cycle, and 1966 cycles in which the discharge capacity is lower than 80%.

Comparative Example 3

The preparation method of the metal ion battery (1) described in Comparative Example 1 was carried out, except that the electrolyte composition (14) was replaced by the electrolyte composition (1) to obtain a metal ion battery (14).

Next, the coulombic efficiency of the metal-ion battery (14), the capacity retention rate at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is lower than 80% were measured in the above-mentioned manner. The results are shown in Table 2.

Examples 12-16

The preparation method of the metal ion battery (1) in Comparative Example 1 was carried out, except that the electrolyte composition (15)-(19) was replaced by the electrolyte composition (1), respectively, to obtain the metal ion battery (15)-(19).

Next, the coulombic efficiencies of the metal-ion batteries (15)-(19), the capacity retention rates at the 2000th cycle and the 3000th cycle, and the number of cycles at which the discharge capacity is lower than 80% were measured, respectively, and the results are shown in the table 2 shown.

Table 2

Take the original aluminum foil used as the negative electrode of the aforementioned metal ion battery, the aluminum negative electrode of the metal ion battery (1) after 3000 charge-discharge cycles, and the aluminum negative electrode of the metal ion battery (8) after 3000 charge-discharge cycles. An electron microscope instrument (model: SU8010) performed surface photography, and the results are shown in Fig. 2, Fig. 3, and Fig. 4, respectively. As can be seen from Figures 2 to 4, the surface of the aluminum foil is smooth before use. After 3000 charge-discharge cycles are assembled into a battery, if the battery without additives is added to the electrolyte composition, the surface of the aluminum electrode obtained after 3,000 charge-discharge cycles is uneven and pitted. In addition, if a nitrogen-containing heterocyclic compound additive is added to the electrolyte composition, the surface of the obtained aluminum electrode remains smooth after 3000 charge-discharge cycles. It is obvious that the addition of nitrogen-containing heterocyclic compound additives to the electrolyte composition can make the metal ion battery (such as aluminum ion battery) uniform during the charge-discharge cycle of the metal electrode terminal. It also improves the self-corrosion of the aluminum electrode surface. effect.

Although the present disclosure has been disclosed above with several embodiments, it is not intended to limit the present disclosure. Anyone with ordinary knowledge in the technical field may make any changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of this disclosure should be determined by the scope of the appended patent application.

10: Positive pole

12: negative pole

14: Isolation film

20: Electrolyte composition

100: Metal-ion battery

Claims (13)

An electrolyte composition for an aluminum ion battery, comprising: a metal salt having a structure represented by formula (I); M _i X _j formula (I) wherein M is aluminum ion; X is F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , CF ₃ SO ₃ ^- , NO ₃ ^- , CH ₃ CO ₂ ^- , SO ₄ ^2- , C ₂ O ₄ ^2- , or [B(C ₂ O ₄ ) ₂ ] ^- ; and, i is 1, 2, 3, 4, 5, or 6; j is 1, 2, 3, 4, 5, or 6; an ion liquid; and an additive, wherein the additive comprises a substituted or unsubstituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compound, wherein the unsubstituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compound is a pyrazole (pyrazole), imidazole ( imidazole), oxazole (Oxazole), isoxazole (isoxazole), thiazole (thiazole), benzimdazole (benzimdazole), indole (indole), indoline (indoline), carbazole (carbazole), pyridazine ( pyridazine, pyrimidine, pyrazine, purine, acridine, phenazine, phenothiazine, quinolone, isoquinoline quinolone), pteridine (pteridine), 1,10-phenanthroline (1,10-phenanthroline), 1,7-phenanthroline (1,7-phenanthroline), 4,7-phenanthroline (4,7 -phenanthroline), 3,4,7,8-tetramethyl-1,10-phenanthroline (3,4,7,8-tetramethyl-1,10-phenanthroline), 4,7-dihydroxy-1, 10-phenanthroline (4,7-dihydroxy-1,10-phenanthroline), 5,6-dimethyl-1,10-phenanthroline (5,6-dimethyl-1,10-phenanthroline), 5- Chloro-1,10-phenanthroline (5-chloro-1,10-phenanthroline), 1,10-phenanthroline-5,6-dione (1,10-phenanthroline-5,6-dione), 1 ,10-phenanthroline monohydrate (1,10-phenanthroline monohydrate), 1,10-phenanthroline hydrochloride monohydrate (1,10-phenanthroline monohydro chloride monohydrate), or a combination of the above. The electrolyte composition for an aluminum ion battery as described in claim 1, wherein the molar ratio of the metal salt to the ionic liquid is 1.0 to 2.05. The electrolyte composition for aluminum ion battery as described in item 1 of the claimed scope, wherein the content of the additive is 0.05wt% to 20wt%, based on the total weight of the metal salt and the ionic liquid. The electrolyte composition for an aluminum ion battery as described in claim 3, wherein the substituted C ₅ -C ₃₀ nitrogen-containing heterocyclic compound refers to at least one of the C ₅ -C ₃₀ nitrogen-containing heterocyclic compounds The hydrogen on the carbon atom is replaced by R, wherein R is halogen, cyano, C _1-10 alkyl, C _1-10 alkoxy, C _1-5 aminoalkyl, -NR ¹ R ² ,

,or

, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently hydrogen or C _1-10 alkyl. The electrolyte composition for an aluminum ion battery as described in claim 1, wherein the additive comprises 4-pyridinecarboxylic acid hydrazide, 3-pyridinecarboxylic acid hydrazide ), 4-pyridyl hydrazide, 4-pyridinecarboxaldehyde, 4-methoxypyridine, 3-methoxypyridine, 2- 2-methoxypyridine, 4-aminopyridine, 4-(aminomethyl)pyridine, pyridine-4-carboxamide, 3- Pyridine-3-carboxamide, pyridine-2-carboxamide, pyridine-3-carboxylic acid, Gena Green B (8-(4- Dimethylaminophenyl)diazenyl-N,N-diethyl-10-phenylphenazin-10-ium-2-amine chloride), or a combination of the above. The electrolyte composition for an aluminum ion battery as described in the first item of the patent application, wherein the ionic liquid has a structure represented by formula (II); [A] _k [B] _l formula (II) wherein, A is imidazolium cation, pyrrolium cation, pyrrolinium cation, pyrrolidinium cation, pyridinium cation, ammonium cation, indium Indazolium cation, pyrimidinium cation, azaannulenium cation, azathiazolium cation, benzimidazolium cation, benzofuran benzofuranium cation, benzotriazolium cation, borolium cation, choline cation, cinnolinium cation, diazepine Diazabicyclodecenium cation, diazabicyclononenium cation, diazabicyclo-undecenium cation, dithiazolium cation ), furanium cation, guanidinium cation, indolinium cation, indolium cation, morpholinium cation, oxaborium Cyclopentenium cation (oxaborolium cation), oxaphospholium cation (oxaphospholium cation), oxazinium cation (oxazinium cation), oxazolium cation (oxazolium cation), isoxazolium cation (iso-oxazolium cation) cation), oxathiazolium cation (oxathiazolium cation), pentazolium cation (pentazolium c cation), phospholium cation, phosphonium cation, phthalazinium cation, piperazinium cation, piperidinium cation, Pyranium cation, pyrazinium cation, pyrazolium cation, pyridazinium cation, quinazolinium cation, quinolinium cation (quinolinium cation), iso-quinolinium cation (iso-quinolinium cation), quinoxalinium cation (quinoxalinium cation), selenozolium cation (selenozolium cation), sulfonium cation (sulfonium cation), tetrazolium cation cation), iso-thiadiazolium cation, thiazinium cation, thiazolium cation, thiophenium cation, thiuronium cation, triazadecenium cation, triazinium cation, triazolium cation, iso-triazolium cation, or uronium cation ); B series F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , [(CF ₃ SO ₂ ) ₂ N] ^- , CF ₃ SO ₃ ^- , NO ₃ ^- , CH ₃ CO ₂ ^- , SO ₄ ^2- , C ₂ O ₄ ^2- , or [B(C ₂ O ₄ ) ₂ ] ^- ; and, k is 1, 2, 3, 4, 5, or 6; l is 1, 2, 3, 4, 5, or 6. The electrolyte composition for an aluminum ion battery as described in item 1 of the claimed scope further comprises a solvent. An aluminum ion battery, comprising: a positive electrode; a separator; a negative electrode, wherein the negative electrode comprises a negative electrode active material, wherein the negative electrode active material is aluminum or an aluminum alloy, wherein the negative electrode is separated from the positive electrode by a separator; and The electrolyte composition for an aluminum ion battery described in any one of items 1 to 7 of the scope of the application is provided between the positive electrode and the negative electrode. The aluminum ion battery as described in claim 8, wherein the positive electrode comprises a positive electrode active material and a positive electrode current collecting layer. The aluminum ion battery of claim 9, wherein the positive electrode collector layer comprises a conductive carbon substrate, a metal material, a metal material with a porous structure, or a combination thereof. The aluminum ion battery as described in claim 9, wherein the positive electrode active material is a carbon material with a layered structure, layered double hydroxide, layered oxide, layered chalcogenide (layered chalcogenide), vanadium oxide, metal sulfide, or a combination of the above. The aluminum ion battery as described in item 8 of the patent application scope, wherein the negative electrode further comprises a negative electrode current collecting layer, and the negative electrode current collecting layer comprises a conductive carbon substrate, lithium mesh, lithium foil, foamed lithium, sodium mesh, Sodium foil, sodium foam, potassium mesh, potassium foil, potassium foam, beryllium mesh, beryllium foil, beryllium foam, magnesium mesh, magnesium foil, magnesium foam, calcium mesh, calcium foil, calcium foam, scandium mesh, Scandium foil, foamed scandium, yttrium mesh, yttrium foil, foamed yttrium, titanium mesh, titanium foil, foamed titanium, zirconium mesh, zirconium foil, foamed zirconium, hafnium mesh, hafnium foil, foamed hafnium, vanadium mesh, Vanadium foil, foamed vanadium, niobium mesh, niobium foil, foamed niobium, tantalum mesh, tantalum foil, foamed tantalum, chromium mesh, chromium foil, foamed chromium, molybdenum mesh, molybdenum foil, foamed molybdenum, tungsten mesh, Tungsten foil, foamed tungsten, manganese mesh, manganese foil, foamed manganese, nickel mesh, metallized foil, expanded metallurgy, rhenium mesh, rhenium foil, foamed rhenium, iron mesh, iron foil, foamed iron, ruthenium mesh, Ruthenium foil, foamed ruthenium, osmium mesh, osmium foil, foamed osmium, cobalt mesh, cobalt foil, foamed cobalt, rhodium mesh, rhodium foil, foamed rhodium, iridium mesh, iridium foil, foamed iridium, nickel mesh, Nickel foil, foamed nickel, palladium mesh, Palladium foil, foamed palladium, platinum mesh, platinum foil, foamed platinum, copper mesh, copper foil, foamed copper, silver mesh, silver foil, foamed silver, gold mesh, gold foil, foamed gold, zinc mesh, zinc foil, Foamed zinc, cadmium mesh, cadmium foil, foamed cadmium, indium mesh, indium foil, foamed indium, thallium mesh, thallium foil, foamed thallium, tin mesh, tin foil, foamed tin, lead mesh, lead foil, hair Foamed lead, antimony mesh, antimony foil, foamed antimony, bismuth mesh, bismuth foil, foamed bismuth, gallium mesh, gallium foil, foamed gallium, aluminum mesh, aluminum foil, foamed aluminum, titanium nitride, conductive polymer, or a combination of the above. According to the aluminum ion battery described in item 8 of the patent application scope, the separator is made of glass fiber, polyethylene (PE), polypropylene (Polypropylene, PP), non-woven fabric, wood fiber, polyether resin (Poly (ether) sulfones), PES), ceramic fibers, or a combination of the above.

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