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CN105226252A - A kind of LNCM-LFMP composite positive pole and preparation method thereof - Google Patents

A kind of LNCM-LFMP composite positive pole and preparation method thereof Download PDF

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Publication number
CN105226252A
CN105226252A CN201510631354.0A CN201510631354A CN105226252A CN 105226252 A CN105226252 A CN 105226252A CN 201510631354 A CN201510631354 A CN 201510631354A CN 105226252 A CN105226252 A CN 105226252A
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lncm
lfmp
positive pole
composite positive
lini
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游才印
王钦
徐可
张卫华
郭少华
杨蓉
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Xian University of Technology
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Xian University of Technology
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Abstract

The invention discloses a kind of LNCM-LFMP composite positive pole, by LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4composition, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1.The invention also discloses the preparation method of this LNCM-LFMP composite positive pole, two components mixed and adds ball grinder ball milling 1 ~ 4h, namely obtaining LNCM-LFMP composite positive pole.In high power charging-discharging process, because the internal resistance of stable other positive electrode of high rate capability is little and stable, bear main diverter function, suppress overvoltage, the overcurrent charge and discharge process of tertiary cathode basis material, therefore composite positive pole of the present invention has stable high rate capability and circulation volume conservation rate, under 2C multiplying power, first discharge specific capacity is at more than 100mAh/g, and 50 circulation Posterior circle capability retentions, more than 80%, are much better than single ternary system LNCM material.

Description

A kind of LNCM-LFMP composite positive pole and preparation method thereof
Technical field
The invention belongs to the preparing technical field of lithium-ion energy storage battery positive electrode, be specifically related to a kind of LNCM-LFMP composite positive pole, also relate to the preparation method of this LNCM-LFMP composite positive pole.
Background technology
Since first Japanese Sony company in 1991 introduces lithium ion battery to the market application, lithium ion battery has been widely used in the portable electric appts such as mobile phone, notebook computer, digital product.Compared with the rechargeable battery of other types, lithium ion battery has high voltage, high-energy-density, low self-discharge rate, the wide advantage such as serviceability temperature scope, memory-less effect.Along with the development of information age and progress and the harsher requirement of energy environment protection, lithium ion battery also shows wide application prospect gradually as Prospect of EVS Powered with Batteries.Meanwhile people also have higher requirement to performance of lithium ion battery, and the research and development of positive electrode become one of key technology of development high performance lithium ion battery.
Ternary system anode material LiNi 1-x-yco xmn yo 2(LNCM) because having the advantages such as high theoretical specific capacity (275mAh/g), good thermal stability and lower production cost, the focus of research was become in recent years.But there is high rate capability difference and the problem such as cycle performance is not good in this material, thus limits its large-scale application.In order to improve the stability of the high rate capability of positive electrode, general method is the Surface coating of positive electrode, and the method relate to extra treatment process, and the acid-base value of malleable positive electrode self, affect serviceability.
Summary of the invention
The object of this invention is to provide a kind of LNCM-LFMP composite positive pole, this material, based on shunting principle, solves the problem that existing ternary system anode material LNCM high rate capability is poor and cycle performance is not good.
Another object of the present invention is to provide the preparation method of above-mentioned LNCM-LFMP composite positive pole.
A technical scheme of the present invention is that a kind of LNCM-LFMP composite positive pole, by LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4composition, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1.
LNCM represents LiNi 1-x-yco xmn yo 2, LFMP represents Li (Fe 1-zmn z) PO 4.
Preferably, in LNCM-LFMP composite positive pole of the present invention, LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4mass percent be respectively 70-99% and 1-30%, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1, the quality summation of above two components is 100%.
Another technical scheme of the present invention is, the preparation method of above-mentioned LNCM-LFMP composite positive pole, is mixed by LNCM and LFMP and adds ball grinder ball milling 1 ~ 4h, obtaining LNCM-LFMP composite positive pole.
Preferably, the mass percent of above-mentioned LNCM and LFMP is respectively 70-99% and 1-30%, and the quality summation of above two components is 100%.
Preferably, above-mentioned LNCM is prepared by high temperature solid phase synthesis, specifically comprises the following steps: with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to following molar ratio weighing, Li +: Ni 2+: Co 2+: Mn 2+=1:(1-x-y): x:y, x=1/5 ~ 1/3, y=1/3 ~ 3/5; Then each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, ball milling 6h is dried and is obtained precursor powder; Finally in Muffle furnace, high temperature sintering is carried out to precursor powder, obtain tertiary cathode material LNCM.
Preferably, high temperature sintering is specially: in air atmosphere, carries out 900 DEG C of high temperature solid-phase sintering 8h, obtain tertiary cathode material LNCM after cooling to precursor powder.
Preferably, above-mentioned LFMP is prepared by carbothermic method, specifically comprises the following steps: with Li 2cO 3, MnCO 3, FeC 2o 42H 2o and NH 4h 2pO 4for raw material, by following molar ratio weighing, Li +: Fe 2+: Mn 2+: P 5+=1:(1-z): z:1, z=0 ~ 1; Then each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, ball milling 4h is dried and is obtained precursor powder; Finally in heat-treatment furnace, high temperature sintering is carried out to precursor powder, obtain positive electrode LFMP.
Preferably, high temperature sintering is specially: at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 9h.
The simplified model of circuit in the parallel connection that present invention utilizes LNCM tertiary cathode material particle composition, and electric current tends to the general principle flowing to the minimum circuit of resistance, thus by adding the LFMP positive electrode generation shunt effect of low internal resistance, high rate capability stable (namely under big current, performance degradation is slow), improve the high rate capability of matrix LNCM positive electrode.
For constant current charge process, with reference to figure 1, composite positive pole is by high resistance R 1and the matrix of high rate capability difference, and low resistance R 2and the positive electrode of high rate capability excellence composition.During charging process there is de-lithium behavior in positive electrode, also namely approximately defines two Li in parallel +ion transfer circuit, its electric current and resistance are respectively I 1, I 2, R 1and R 2.In constant current charge process, negative electrical charge e is to negative pole displacement, if can not in time and positive pole move to the Li of negative pole +combine, will negative pole be accumulated in, increase the electrical potential difference between both positive and negative polarity, until overcharge inefficacy.More powerful discharge and recharge, namely adopts higher charging and discharging currents I, if its current increment is Δ I, then compute matrix is as follows with point current value adding positive electrode:
ΔI 1 = Δ I × R 2 R 1 + R 2 - - - ( 1 )
ΔI 2 = Δ I × R 1 R 1 + R 2 - - - ( 2 )
In formula:
Δ I 1the electric current that-basis material LNCM bears, A;
Δ I 2-the electric current that bears of second-phase material LFMP that adds, A;
Δ I-transient state overcharges electric current, A;
R 1the resistance of-basis material, Ω;
R 2the resistance of the second-phase material of-introducing, Ω.
From above-mentioned equation, add positive electrode R 2resistance is less, the overcurrent Δ I that basis material LNCM bears 1impact less, its high power capacity more can be played, and makes composite positive pole show excellent high rate capability (also can bear high current charge-discharge I).
Based on above-mentioned dividing technology principle, with LiNi 1-x-yco xmn yo 2(x=1/5 ~ 1/3, y=1/3 ~ 3/5) (LNCM) is basis material, with Li (Fe 1-zmn z) PO 4(z=0 ~ 1) (LFMP) is second-phase adding material, develops the LNCM-LFMP composite positive pole that the present invention can improve the high magnification chemical property of ternary system anode material.Material of the present invention adopts mechanical activation-high temperature solid-state method to prepare the high layer structure LNCM of purity as positive electrode matrix, adopts carbothermic method to prepare LFMP as second-phase adding material, then obtains LNCM-LFMP composite positive pole by mechanical blending.
The invention has the beneficial effects as follows: (1) LNCM-LFMP of the present invention composite positive pole make use of the shunting action of the stable LFMP positive electrode of high rate capability, inhibit the phenomenon that the chemical property under the big current of high power capacity ternary system anode material LNCM in high power charging-discharging process sharply worsens, give full play to the advantage of ternary system LNCM high power capacity, high circulation volume conservation rate, there is excellent high rate capability and cyclical stability.Experiment prove LNCM-LFMP composite positive pole of the present invention under 2C multiplying power first discharge specific capacity at more than 100mAh/g.50 circulation Posterior circle capability retentions, more than 80%, are much better than single ternary system LNCM material.(2) preparation method of LNCM-LFMP composite positive pole of the present invention is simple, compared to existing surface coating method, avoids extra surface modification processes and other negative effect to positive electrode thereof.
Accompanying drawing explanation
Fig. 1 is the dividing technology schematic diagram of LNCM-LFMP composite positive pole of the present invention;
Fig. 2 is LiNi in the embodiment of the present invention 1 1/3co 1/3mn 1/3o 2xRD collection of illustrative plates;
Fig. 3 is Li (Fe in embodiment of the present invention 1-3 1-zmn z) PO 4xRD contrast collection of illustrative plates;
Fig. 4 is the high rate cyclic specific discharge capacity figure of six kinds of composite positive poles of the embodiment of the present invention 1;
Fig. 5 is the high rate cyclic specific discharge capacity figure of the composite positive pole of the embodiment of the present invention 2;
Fig. 6 is the high rate cyclic specific discharge capacity figure of the composite positive pole of the embodiment of the present invention 3.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
The invention provides a kind of LNCM-LFMP composite positive pole, by LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4composition, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1.
Preferably, LNCM-LFMP composite positive pole of the present invention is the LiNi of 70-99% by mass percent 1-x-yco xmn yo 2with the Li (Fe of 1-30% 1-zmn z) PO 4composition, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1, the quality summation of above two components is 100%.
Present invention also offers the preparation method of above-mentioned LNCM-LFMP composite positive pole, LNCM and LFMP mixed and adds ball grinder ball milling 1 ~ 4h, obtaining LNCM-LFMP composite positive pole.
Preferably, the mass percent of above-mentioned LNCM and LFMP is respectively 70-99% and 1-30%, and the quality summation of above two components is 100%.
Preferably, above-mentioned LNCM is prepared by high temperature solid phase synthesis, specifically comprises the following steps: with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to following molar ratio weighing, Li +: Ni 2+: Co 2+: Mn 2+=1:(1-x-y): x:y, x=1/5 ~ 1/3, y=1/3 ~ 3/5; Then each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, ball milling 6h is dried and is obtained precursor powder; Finally in Muffle furnace, high temperature sintering is carried out to precursor powder, after cooling, obtain tertiary cathode material LNCM (LiNi 1-x-yco xmn yo 2).
Preferably, high temperature sintering is specially: in air atmosphere, carries out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder.
Preferably, above-mentioned LFMP is prepared by carbothermic method, specifically comprises the following steps: with Li 2cO 3, MnCO 3, FeC 2o 42H 2o, NH 4h 2pO 4for raw material, by following molar ratio weighing, Li +: Fe 2+: Mn 2+: P 5+=1:(1-z): z:1, z=0 ~ 1; Then each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, ball milling 4h is dried and is obtained precursor powder; Finally in heat-treatment furnace, high temperature sintering is carried out to precursor powder, obtain positive electrode LFMP (Li (Fe 1-zmn z) PO 4).
Preferably, high temperature sintering is specially: at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 8-9h.
Embodiment 1
Prepare a kind of LNCM-LFMP composite positive pole, implement according to following steps:
Step 1, with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to mol ratio Li +: Ni 2+: Co 2+: Mn 2+=1:1/3:1/3:1/3 (x=1/3, y=1/3) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with appropriate absolute ethyl alcohol, seal ball milling 6h in ball grinder, cools and dry to obtain precursor powder; In air atmosphere, be placed in Muffle furnace and carry out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder, after cooling, grinding distribution obtains tertiary cathode material LiNi 1/3co 1/3mn 1/3o 2(LNCM).
Step 2, with Li 2cO 3, FeC 2o 42H 2o, MnCO 3, NH 4h 2pO 4for raw material, Li in molar ratio +: Fe 2+: Mn 2+: P 5+=1:0.4:0.6:1 (z=0.6) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, seal ball milling 4h in ball grinder, cools and dry to obtain precursor powder; Last at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 8h (programming rate 10 DEG C/min) in heat-treatment furnace, obtain positive electrode LiFe 0.4mn 0.6pO 4(LFMP).
Step 3, by above-mentioned LiNi 1/3co 1/3mn 1/3o 2and LiFe 0.4mn 0.6pO 4be respectively 90% and 10% according to mass percent to mix, add ball milling 4h in ball grinder, namely obtain the LNCM-LFMP composite positive pole of mass ratio 9:1.
Embodiment 2
Prepare a kind of LNCM-LFP composite positive pole, implement according to following steps:
Step 1, with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to mol ratio Li +: Ni 2+: Co 2+: Mn 2+=1:1/3:1/3:1/3 (x=1/3, y=1/3) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with appropriate absolute ethyl alcohol, seal ball milling 6h in ball grinder, cools and dry to obtain precursor powder; In air atmosphere, be placed in Muffle furnace and carry out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder, after cooling, grinding distribution obtains tertiary cathode material LiNi 1/3co 1/3mn 1/3o 2(LNCM).
Step 2, with Li 2cO 3, FeC 2o 42H 2o, NH 4h 2pO 4for raw material, Li in molar ratio +: Fe 2+: P 5+=1:1:1 (z=0) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, seal ball milling 4h in ball grinder, cools and dry to obtain precursor powder; Last at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 9h (programming rate 10 DEG C/min) in heat-treatment furnace, obtain positive electrode LiFePO 4(LFP).
Step 3, by above-mentioned LiNi 1/3co 1/3mn 1/3o 2and LiFePO 4be respectively 90% and 10% according to mass percent to mix, add ball milling 4h in ball grinder, namely obtain the LNCM-LFP composite positive pole of mass ratio 9:1.
In the present embodiment, Li (Fe 1-zmn z) PO 4middle z=0, therefore not containing Mn element, therefore LFMP is abbreviated as LFP.
Embodiment 3
Prepare a kind of LNCM-LMP composite positive pole, implement according to following steps:
Step 1, with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to mol ratio Li +: Ni 2+: Co 2+: Mn 2+=1:1/3:1/3:1/3 (x=1/3, y=1/3) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with appropriate absolute ethyl alcohol, seal ball milling 6h in ball grinder, cools and dry to obtain precursor powder; In air atmosphere, be placed in Muffle furnace and carry out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder, after cooling, grinding distribution obtains tertiary cathode material LiNi 1/3co 1/3mn 1/3o 2(LNCM).
Step 2, with Li 2cO 3, MnCO 3, NH 4h 2pO 4for raw material, Li in molar ratio +: Mn 2+: P 5+=1:1:1 (z=1) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, seal ball milling 4h in ball grinder, cools and dry to obtain precursor powder; Last at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 9h (programming rate 10 DEG C/min) in heat-treatment furnace, obtain positive electrode LiMnPO 4(LMP).
Step 3, by above-mentioned LiNi 1/3co 1/3mn 1/3o 2and LiMnPO 4be respectively 90% and 10% according to mass percent to mix, add ball milling 4h in ball grinder, namely obtain the LNCM-LMP composite positive pole of mass ratio 9:1.
In the present embodiment, Li (Fe 1-zmn z) PO 4middle z=1, therefore not containing Fe element, therefore LFMP is abbreviated as LMP.
Embodiment 4
Prepare a kind of LNCM-LFMP composite positive pole, implement according to following steps:
Step 1, with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to mol ratio Li +: Ni 2+: Co 2+: Mn 2+=1:1/5:1/5:3/5 (x=1/5, y=3/5) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with appropriate absolute ethyl alcohol, seal ball milling 6h in ball grinder, cools and dry to obtain precursor powder; In air atmosphere, be placed in Muffle furnace and carry out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder, after cooling, grinding distribution obtains tertiary cathode material LiNi 1/5co 1/5mn 3/5o 2(LNCM).
Step 2, with Li 2cO 3, FeC 2o 42H 2o, MnCO 3, NH 4h 2pO 4for raw material, Li in molar ratio +: Fe 2+: Mn 2+: P 5+=1:0.2:0.8:1 (z=0.8) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, seal ball milling 4h in ball grinder, cools and dry to obtain precursor powder; Last at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 9h (programming rate 10 DEG C/min) in heat-treatment furnace, obtain positive electrode LiFe 0.2mn 0.8pO 4(LFMP).
Step 3, by above-mentioned LiNi 1/5co 1/5mn 3/5o 2and LiFe 0.2mn 0.8pO 4be respectively 80% and 20% according to mass percent to mix, add ball milling 4h in ball grinder, namely obtain the LNCM-LFMP composite positive pole of mass ratio 8:2.
Embodiment 5
Prepare a kind of LNCM-LFMP composite positive pole, implement according to following steps:
Step 1, with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to mol ratio Li +: Ni 2+: Co 2+: Mn 2+=1:2/5:1/5:2/5 (x=1/5, y=2/5) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with appropriate absolute ethyl alcohol, seal ball milling 6h in ball grinder, cools and dry to obtain precursor powder; In air atmosphere, be placed in Muffle furnace and carry out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder, after cooling, grinding distribution obtains tertiary cathode material LiNi 2/5co 1/5mn 2/5o 2(LNCM).
Step 2, with Li 2cO 3, FeC 2o 42H 2o, MnCO 3, NH 4h 2pO 4for raw material, Li in molar ratio +: Fe 2+: Mn 2+: P 5+=1:0.6:0.4:1 (z=0.4) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, seal ball milling 4h in ball grinder, cools and dry to obtain precursor powder; Last at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 9h (programming rate 10 DEG C/min) in heat-treatment furnace, obtain positive electrode LiFe 0.6mn 0.4pO 4(LFMP).
Step 3, by above-mentioned LiNi 2/5co 1/5mn 2/5o 2and LiFe 0.6mn 0.4pO 4be respectively 70% and 30% according to mass percent to mix, add ball milling 4h in ball grinder, namely obtain the LNCM-LFMP composite positive pole of mass ratio 7:3.
Embodiment 6
Prepare a kind of LNCM-LFMP composite positive pole, implement according to following steps:
Step 1, with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to mol ratio Li +: Ni 2+: Co 2+: Mn 2+=1:1/3:1/3:1/3 (x=1/3, y=1/3) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with appropriate absolute ethyl alcohol, seal ball milling 6h in ball grinder, cools and dry to obtain precursor powder; In air atmosphere, be placed in Muffle furnace and carry out 900 DEG C of high temperature solid-phase sintering 8h to precursor powder, after cooling, grinding distribution obtains tertiary cathode material LiNi 1/3co 1/3mn 1/3o 2(LNCM).
Step 2, with Li 2cO 3, FeC 2o 42H 2o, MnCO 3, NH 4h 2pO 4for raw material, Li in molar ratio +: Fe 2+: Mn 2+: P 5+=1:0.4:0.6:1 (z=0.6) weighs, and after mixing, each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, seal ball milling 4h in ball grinder, cools and dry to obtain precursor powder; Last at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 8h (programming rate 10 DEG C/min) in heat-treatment furnace, obtain positive electrode LiFe 0.4mn 0.6pO 4(LFMP).
Step 3, by above-mentioned LiNi 1/3co 1/3mn 1/3o 2and LiFe 0.4mn 0.6pO 4be respectively 99% and 1% according to mass percent to mix, add ball milling 4h in ball grinder, namely obtain the LNCM-LFMP composite positive pole of mass ratio 99:1.
Performance Detection is carried out to the material that above section Example is prepared, so that the beneficial effect of material of the present invention to be described.
By detecting the LiNi of embodiment 1 1/3co 1/3mn 1/3o 2(LNCM) XRD collection of illustrative plates, as shown in Figure 2, can find out LiNi of the present invention 1/3co 1/3mn 1/3o 2(LNCM) there is the layer structure of highly crystalline.In addition, by detecting LiFe in embodiment 1 0.4mn 0.6pO 4(LFMP), LiFePO in embodiment 2 4(LFP) LiMnPO and in embodiment 3 4(LMP) XRD collection of illustrative plates, as shown in Figure 3, can find out Li (Fe of the present invention 1-zmn z) PO 4there is the olivine-type structure of highly crystalline.
Six groups of LNCM-LFMP composite positive poles that mass ratio is followed successively by 9:1,8:2,7:3,92:8,95:5 and 98:2 are prepared respectively according to the preparation method of embodiment 1, employing acetylene black is conductive agent, polyvinylidene fluoride PVDF is binding agent, NMP is solvent, Celgard2400 is barrier film, take metal lithium sheet as negative pole, with each LNCM-LFP composite positive pole of embodiment 1 for positive pole, with LiPF6, ((EC+DEC), for electrolyte, is assembled into CR2032 type battery testing sample.With single LNCM and single LFMP for control group, detect its initial discharge specific capacity in test voltage scope 2.5-4.5V under 2C multiplying power and circulation volume conservation rate curve thereof.As shown in Figure 4, six kinds of LNCM-LFMP composite positive poles that embodiment 1 is prepared all demonstrate good high-rate charge-discharge capability and cyclical stability to result.Such as, after lower 50 circulations of 2C multiplying power, single tertiary cathode material LiNi 1/3co 1/3mn 1/3o 2(LNCM) specific discharge capacity decays to 53mAh/g, and the LNCM-LFMP composite positive pole adding the LFMP of mass fraction 10% (mass ratio 9:1) circulates 50 times under 2C multiplying power, its specific discharge capacity still keeps 110mAh/g, is about 2 times of single ternary material LNCM.Add the circulation-specific capacity of 30% quality (mass ratio 7:3) LFMP composite positive pole under 2C and be far superior to single LNCM, first discharge specific capacity is 118.4mAh/g, and 50 times circulation volume conservation rate is 89.3%.
The mass ratio that in like manner testing example 2 is prepared is initial discharge specific capacity in test voltage scope 2.5-4.5V under 2C multiplying power of the LNCM-LFP composite positive pole of 9:1 and circulation volume conservation rate curve thereof.As shown in Figure 5, the first discharge specific capacity of LNCM-LFP composite positive pole is 115.2mAh/g to result, and after 50 circulations, capacity remains 80.9mAh/g, is far superior to the capacity 54.6mAh/g of single LNCM.
The mass ratio that in like manner testing example 3 is prepared is initial discharge specific capacity in test voltage scope 2.5-4.5V under 2C multiplying power of the LNCM-LMP composite positive pole of 9:1 and circulation volume conservation rate curve thereof.As shown in Figure 6, first discharge specific capacity is 100.6mAh/g to result, and after 50 circulations, capacity remains 95.2mAh/g, is far superior to the battery performance of single LNCM (54.6mAh/g) and single LMP (50.3mAh/g).
First discharge specific capacity is all at more than 100mAh/g under 2C multiplying power for the LNCM-LFMP composite positive pole of other embodiment, and 50 circulation Posterior circle capability retentions, more than 80%, are much better than single ternary system LNCM material.
Above test result absolutely proves in high power charging-discharging process, because the internal resistance of the stable LFMP positive electrode of high rate capability is little and stable, bear main diverter function, suppress overvoltage, the overcurrent charge and discharge process of LNCM tertiary cathode basis material, thus obtain stable high rate capability and circulation volume conservation rate.LFMP material is mixed, the high magnification capacity that composite positive pole display is excellent and cyclical stability in LNCM tertiary cathode material.Further, the preparation method of LNCM-LFMP composite positive pole of the present invention is simple, compared to existing surface coating method, avoids extra surface modification processes and other negative effect to positive electrode thereof.
More than the present invention describe just section Example, but the present invention is not limited to above-mentioned embodiment.Above-mentioned embodiment is schematic, is not restrictive.Every employing materials and methods of the present invention, do not departing under the ambit that present inventive concept and claim protect, all concrete expansions all belong within protection scope of the present invention.

Claims (8)

1. a LNCM-LFMP composite positive pole, is characterized in that, by LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4composition, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1.
2. LNCM-LFMP composite positive pole according to claim 1, is characterized in that, described LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4mass percent be respectively 70-99% and 1-30%, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1, the quality summation of above two components is 100%.
3. prepare a method for LNCM-LFMP composite positive pole described in claim 1, it is characterized in that, by LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4mix and add ball grinder ball milling 1 ~ 4h, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1, to LNCM-LFMP composite positive pole.
4. the preparation method of LNCM-LFMP composite positive pole according to claim 3, is characterized in that, described LiNi 1-x-yco xmn yo 2with Li (Fe 1-zmn z) PO 4mass percent be respectively 70-99% and 1-30%, wherein, x=1/5 ~ 1/3, y=1/3 ~ 3/5, z=0 ~ 1, the quality summation of above two components is 100%.
5. the preparation method of LNCM-LFMP composite positive pole according to claim 3, is characterized in that, described LiNi 1-x-yco xmn yo 2prepared by high temperature solid phase synthesis, specifically comprise the following steps: with Li 2cO 3, 2CoCO 33Co (OH) 2h 2o, NiCO 32Ni (OH) 24H 2o and MnCO 3for raw material, according to following molar ratio weighing, Li +: Ni 2+: Co 2+: Mn 2+=1:(1-x-y): x:y, x=1/5 ~ 1/3, y=1/3 ~ 3/5; Then each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, ball milling 6h is dried and is obtained precursor powder; Finally in Muffle furnace, high temperature sintering is carried out to precursor powder, obtain tertiary cathode material LiNi 1-x-yco xmn yo 2.
6. the preparation method of LNCM-LFMP composite positive pole according to claim 5, is characterized in that, described high temperature sintering is specially: in air atmosphere, carries out 900 DEG C of high temperature solid-phase sintering 8h, obtain tertiary cathode material LNCM after cooling to precursor powder.
7. the preparation method of LNCM-LFMP composite positive pole according to claim 3, is characterized in that, described Li (Fe 1-zmn z) PO 4prepared by carbothermic method, specifically comprise the following steps: with Li 2cO 3, MnCO 3, FeC 2o 42H 2o and NH 4h 2pO 4for raw material, by following molar ratio weighing, Li +: Fe 2+: Mn 2+: P 5+=1:(1-z): z:1, z=0 ~ 1; Then each raw material is placed in ball grinder, does dispersant with absolute ethyl alcohol, ball milling 4h is dried and is obtained precursor powder; Finally in heat-treatment furnace, high temperature sintering is carried out to precursor powder, obtain positive electrode Li (Fe 1-zmn z) PO 4.
8. the preparation method of LNCM-LFMP composite positive pole according to claim 7, is characterized in that, described high temperature sintering is specially: at N 2under atmosphere protection, to precursor powder 700 DEG C annealing 9h.
CN201510631354.0A 2015-09-29 2015-09-29 A kind of LNCM-LFMP composite positive pole and preparation method thereof Pending CN105226252A (en)

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