CN102800866B - A kind of anode additive and the manganese system lithium cell containing this additive - Google Patents

A kind of anode additive and the manganese system lithium cell containing this additive Download PDF

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CN102800866B
CN102800866B CN201210137808.5A CN201210137808A CN102800866B CN 102800866 B CN102800866 B CN 102800866B CN 201210137808 A CN201210137808 A CN 201210137808A CN 102800866 B CN102800866 B CN 102800866B
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battery
additive
present
positive electrode
manganese
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CN102800866A (en
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潘青海
朱菲
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Shangqiu Shenfeng Energy Technology Co.,Ltd.
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Baishun Songtao (tianjin) Battery Technology Development Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a kind of anode additive and the manganese system lithium cell containing this additive.Additive of the present invention is a kind of acid and manganese ion absorbent, and it can with the H in battery +reaction, absorbs the acid in battery, prevents acid corrosion positive electrode, affect the performance of battery; Also can preferentially and the Mn that is dissolved down of positive electrode n+there is chemical reaction, prevent Mn n+move to negative pole generation chemical reaction, reduce the useful life of battery.Additive of the present invention does not change internal structure and the production technology of battery, and cost is lower.Present invention also offers a kind of manganese system lithium cell containing this additive.The present invention effectively can improve battery and battery storage performance, produces good economic benefit.

Description

A kind of anode additive and the manganese system lithium cell containing this additive
Technical field
The present invention relates to a kind of anode additive, for absorbing H free in battery +mn after (hydrogen ion) and positive electrode dissolve n+(manganese ion).
Background technology
Lithium rechargeable battery is a kind of ideal battery of high-energy-density, along with developing rapidly of modern electronic equipment, communication apparatus and electric motor car, more and more higher to the performance requirement of the lithium rechargeable battery as electric power system, domestic and international many battery producers attempt the performance improveing battery by all means.At present the comparatively normal method adopted have raw-material preferably, the method such as the raising in inside battery space.Manganese series lithium ion battery is one of desirable lithium rechargeable battery.
Because a small amount of water can form a small amount of acid in existing manganese based lithium-ion secondary cell, in some inside battery side reaction, also free H can be produced +, H free in battery +meeting corroding electrode material, affects the performance of battery.
The Mn produced after cell positive material dissolves n+move to negative pole generation chemical reaction, the material of generation covers the surface of negative electrode lithium ion passage, blocking channel, affects the chemical property of battery, reduces the useful life of battery.
Patent CN02151025.3 discloses a kind of lithium battery electrolytes and preparation method thereof; Patent CN200380107648.9 discloses a kind of additive of positive electrode of lithium secondary battery, the positive electrode of lithium secondary battery and adopts its positive pole and lithium secondary battery; Patent CN200580017212.X discloses a kind of additive for lithium secondary batteries, and above-mentioned patent all discloses the additive for lithium battery, but the additive disclosed in above-mentioned document can not solve H free in battery +or cell positive material dissolves the rear Mn produced n+move to the problem of negative pole generation chemical reaction blocking channel.
Summary of the invention
The problem to be solved in the present invention be to provide a kind of effectively can improve battery and battery storage performance anode additive and manganese system lithium cell containing this additive.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of anode additive, and the general formula of described additive is:
Li xR yO z；
X: y: z=(0 ~ 1): (1 ~ 2): (1 ~ 4), preferred x: y: z=1: 1: 2;
R is selected from one in Mn, Ti, Fe, Co, Ni, Na, Ca, Al, Mg, S, N, P, B, Bi, Nd or La to three kinds of chemical elements.
Li xr yo zrepresentative example comprises Li below 4ti 5o 12, LiNiO 2, Ni 2o 3, LiNi 2/3co 1/3o 2, LiNi 0.95mg 0.05o 2, LiNi 0.95al 0.05o 2, NiO 2, LiNi 0.95al 0.05o 2, Li (Li 0.01ni 0.19) 5o 2, LiNi 0.97nd 0.03o 2, LiNi 0.98la 0.02o 2, LiMg 0.01ni 0.8mn 0.19o 2with Li (Mg 0.01mn 0.99) 2o 4.
Additive of the present invention is a kind of acid and manganese ion absorbent, and it can with the H in battery +reaction, absorbs the acid in battery, prevents acid corrosion positive electrode, affect the performance of battery; Also can preferentially and the Mn that is dissolved down of positive electrode n+there is chemical reaction, prevent Mn n+move to negative pole generation chemical reaction, the material of generation covers the surface of negative pole passage, blocking channel, affects the chemical property of battery, reduces the useful life of battery.This additive does not change internal structure and the production technology of battery, and cost is lower.
Anode additive Li of the present invention xr yo z, absorb H +a kind of possible chemical equation:
Li xR yO z+qH ++qe -→Li xH qR yO z
Citing is as, Li 4ti 5o 12+ xH ++ xe -=Li 4h xti 5o 12(0 < x < 2)
Absorb Mn n+a kind of possible chemical equation:
Li xR yO z+rMn n++rne -→Li xR yMn rO z
Citing is as, Li 4ti 5o 12+ xMn 2++ 2xe --=Li 4ti 5mn xo 12
Present invention also offers a kind of cell positive material, it contains described anode additive, and preferably, the addition of described anode additive accounts for the 1%-5% of positive electrode quality.Additive is added in positive electrode to the method prepared method that cell positive material adopts and be known to the skilled person, as by pulverous anode additive Li xr yo z, (general 1%-5%) is added in pulverous manganese cathode material according to a certain percentage, then adds bonding agent (NMP), and mix and blend, makes anode sizing agent, is applied on aluminium foil, makes positive electrode.
Present invention also offers a kind of manganese based lithium-ion secondary cell, described battery contains above-mentioned anode additive.
Preferably, the addition of described anode additive accounts for the 1%-5% of positive electrode quality.
Anode additive of the present invention can be applied to the various lithium rechargeable battery containing manganese cathode material.
The general formula of described manganese cathode material is:
Li (M xmn 1-x) 2(O 1-yf y) 4, wherein 0≤x≤0.2; 0≤y≤0.1;
M is one to three kind of the chemical element be selected from Li, Na, Mg, Al, Si, S, K, Ca, Sc, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Sr, Y, Zr, Nb, In, Sn, Ba, La, Ce, Nd, Sm, Ta or Pb;
Li (M xmn 1-x) 2(O 1-yf y) 4representative example comprises LiMn below 2o 4, Li (Mg 0.01mn 0.99) 2(O 0.99f 0.01) 4with Li (Ni bco cmn 1-b-c) 2o 4, wherein 0≤b≤2/3,0≤c≤2/3, b+c≤2/3, citing is as Li (Ni 0.04co 0.02mn 0.94) 2o 4.
Negative material in battery of the present invention there is no particular restriction, as long as be selected from the negative material being applicable to manganese based lithium-ion secondary cell all can realize the present invention, preferably, can be selected from graphite, silicon, ashbury metal or lithium titanate.
Present invention also offers described anode additive containing the application in the lithium rechargeable battery of manganese cathode material.
The advantage that the present invention has and good effect are:
Additive of the present invention does not change internal structure and the production technology of battery, and cost is lower, and the manganese based lithium-ion secondary cell cycle life that with the addition of anode additive of the present invention is longer, and battery storage performance is better.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.In embodiment, the adding proportion of anode additive in positive electrode all refers to mass percent.
Embodiment 1:
The anode additive Li of the present embodiment xr yo zfor Li 4ti 5o 12.
Get in positive electrode and be added with 2%Li 4ti 5o 12liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as A1 and A2 respectively, then gets and do not add Li 4ti 5o 12liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as B1 and B2 respectively, and 4 batteries are used 1C simultaneously in the environment of 55 DEG C, and voltage carries out charge-discharge test from 2.5V to 4.2V.Result of the test is as shown in table 1:
Table 1
Embodiment 2:
The anode additive Li of the present embodiment xr yo zfor NiO 2.
Get in positive electrode the NiO being added with 2% 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as C1 and C2 respectively, then gets and do not add NiO 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as D1 and D2 respectively, is carried out shelving test by 4 batteries under the environment of 55 DEG C simultaneously.Result of the test is as shown in table 2:
Table 2
Embodiment 3:
The anode additive Li of the present embodiment xr yo zfor LiNi 0.95al 0.05o 2.
Get in positive electrode and be added with 3%LiNi 0.95al 0.05o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as E1 and E2 respectively, then gets and do not add LiNi 0.95al 0.05o 2lithium manganate cathode LiMn 2o 4lithium rechargeable battery 2, is labeled as F1 and F2 respectively, and 4 batteries are used 1C simultaneously in the environment of 55 DEG C, and voltage carries out charge-discharge test from 2.5V to 4.2V.Result of the test is as shown in table 3:
Table 3
Embodiment 4:
The anode additive Li of the present embodiment xr yo zfor Li 4ti 5o 12.
Get in positive electrode and be added with 2%Li 4ti 5o 12li (Mg 0.01mn 0.99) 2(O 0.99f 0.01) 4positive pole lithium rechargeable battery 2, is labeled as G1 and G2 respectively, then gets and do not add Li 4ti 5o 12li (Mg 0.01mn 0.99) 2(O 0.99f 0.01) 4 positive pole lithium rechargeable battery 2, be labeled as H1 and H2 respectively, 4 batteries are used 1C simultaneously in the environment of 55 DEG C, and voltage carries out charge-discharge test from 2.5V to 4.2V.Result of the test is as shown in table 4:
Table 4
Embodiment 5:
The anode additive Li of the present embodiment xr yo zfor Ni 2o 3.
Get in positive electrode the N being added with 2% 2iO 3li (Ni 0.04co 0.02mn 0.94) 2o 4positive pole lithium rechargeable battery 2, is labeled as I1 and I2 respectively, then gets and do not add Ni 2o 3li (Ni 0.04co 0.02mn 0.94) 2o 4positive pole lithium rechargeable battery 2, is labeled as J1 and J2 respectively, is carried out shelving test by 4 batteries under the environment of 55 DEG C simultaneously.Result of the test is as shown in table 5:
Table 5
Embodiment 6:
The anode additive Li of the present embodiment xr yo zfor LiNi 0.97nd 0.03o 2.
Get in positive electrode the LiNi being added with 2% 0.97nd 0.03o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as K1 and K2 respectively, then gets and do not add LiNi 0.97nd 0.03o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as L1 and L2 respectively, is carried out shelving test by 4 batteries under the environment of 55 DEG C simultaneously.Result of the test is as shown in table 6:
Table 6
Embodiment 7:
The anode additive Li of the present embodiment xr yo zfor LiNi 0.98la 0.02o 2.
Get in positive electrode and be added with 2%LiNi 0.98la 0.02o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as M1 and M2 respectively, then gets and do not add LiNi 0.98la 0.02o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as N1 and N2 respectively, and 4 batteries are used 1C simultaneously in the environment of 55 DEG C, and voltage carries out charge-discharge test from 2.5V to 4.2V.Result of the test is as shown in table 7:
Table 7
Embodiment 8:
The anode additive Li of the present embodiment xr yo zfor LiMg 0.01ni 0.8mn 0.19o 2.
Get in positive electrode and be added with 2%LiMg 0.01ni 0.8mn 0.19o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as P1 and P2 respectively, then gets and do not add LiMg 0.01ni 0.8mn 0.19o 2liMn2O4 LiMn 2o 4positive pole lithium rechargeable battery 2, is labeled as Q1 and Q2 respectively, and 4 batteries are used 1C simultaneously in the environment of 55 DEG C, and voltage carries out charge-discharge test from 2.5V to 4.2V.Result of the test is as shown in table 8:
Table 8
Result as can be seen from table 1 to table 8, in positive electrode, with the addition of the manganese based lithium-ion secondary cell of additive of the present invention battery cycle life and secondary cell storge quality are all better than the manganese based lithium-ion secondary cell not adding additive of the present invention.
Above preferred embodiment of the present invention has been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.

Claims (1)

1. a manganese based lithium-ion secondary cell, is characterized in that: the positive electrode of battery is manganese cathode material, and containing anode additive, the addition of described anode additive accounts for 2% of positive electrode quality;
Described anode additive is Li 4ti 5o 12, Ni 2o 3, LiNi 0.95mg 0.05o 2, NiO 2, LiNi 0.97nd 0.03o 2, LiNi 0.98la 0.02o 2, LiMg 0.01ni 0.8mn 0.19o 2or Li (Mg 0.01mn 0.99) 2o 4; H in this anode additive and battery +reaction, absorbs the acid in battery, prevents acid corrosion positive electrode, or the Mn that preferential and positive electrode is dissolved down n+there is chemical reaction, prevent Mn n+move to negative pole generation chemical reaction; And described manganese cathode material is LiMn 2o 4, Li (Mg 0.01mn 0.99) 2(O 0.99f 0.01) 4or Li (Ni bco cmn 1-b-c) 2o 4; Described negative material is selected from graphite, silicon, ashbury metal or lithium titanate; Wherein Li (Ni bco cmn 1-b-c) 2o 40≤b≤2/3 need be met, 0≤c≤2/3, b+c≤2/3.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1198022A (en) * 1997-04-24 1998-11-04 松下电器产业株式会社 Non aqueous electrolyte secondary batteries
CN101501897A (en) * 2006-08-10 2009-08-05 奥克斯能源有限公司 A cell or battery with a metal lithium electrode and electrolytes therefor

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KR100412188B1 (en) * 1998-08-27 2003-12-24 닛본 덴끼 가부시끼가이샤 Nonaqueous Electrolyte Secondary Cell
US20050026042A1 (en) * 2003-07-29 2005-02-03 Alain Vallee Polyimide-based battery for a portable electronic appliance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1198022A (en) * 1997-04-24 1998-11-04 松下电器产业株式会社 Non aqueous electrolyte secondary batteries
CN101501897A (en) * 2006-08-10 2009-08-05 奥克斯能源有限公司 A cell or battery with a metal lithium electrode and electrolytes therefor

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