POSITIVE ELECTRODE PLATE, SECONDARY BATTERY, BATTERY MODULE, BATTERY PACK AND POWER CONSUMING DEVICE
A positive electrode plate, a secondary battery, a battery module, a battery pack, and a power consuming device are described. The positive electrode plate include a positive electrode current collector and positive electrode film layers having a single-layer or multi-layer structure. When the positive electrode film layers have a single-layer structure, at least one of the positive electrode film layers comprises a first positive electrode active material and a second positive electrode active material; and/or when the positive electrode film layers have a multi-layer structure, at least one layer of the at least one of the positive electrode film layers comprises the first and second positive electrode active materials; the first positive electrode active material comprises an inner core Li 1+x Mn 1-y A y P 1-z R z O 4 , a first coating layer comprising crystalline pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , a second coating layer comprising crystalline phosphate XPO 4 , and a third coating layer; and the third coating layer is carbon.
1 . A positive electrode plate, comprising a positive electrode current collector and positive electrode film layers provided on at least one surface of the positive electrode current collector; wherein the positive electrode film layers have a single-layer structure or a multi-layer structure; when the positive electrode film layers have a single-layer structure, at least one of the positive electrode film layers comprises both a first positive electrode active material having a core-shell structure and a second positive electrode active material; and/or when the positive electrode film layers have a multi-layer structure, at least one layer of the at least one of the positive electrode film layers comprises both a first positive electrode active material having a core-shell structure and a second positive electrode active material; wherein
the first positive electrode active material comprises an inner core, a first coating layer coating the inner core, a second coating layer coating the first coating layer, and a third coating layer coating the second coating layer; the inner core comprises Li 1+x Mn 1-y A y P 1-z R z O 4 , the first coating layer comprises crystalline pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , the second coating layer comprises crystalline phosphate XPO 4 , and the third coating layer comprises carbon;
wherein
A comprises one or more elements selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge;
R comprises one or more elements selected from B, Si, N and S;
x is selected from any value in the range of −0.100 to 0.100;
y is selected from any value in the range of 0.001 to 0.500;
z is selected from any value in the range of 0.001 to 0.100;
M in the crystalline pyrophosphates Li a MP 2 O 7 and M b (P 2 O 7 ) c each independently comprises one or more elements selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al,
a is selected from any value in the range of 0 to 2;
b is selected from any value in the range of 1 to 4;
c is selected from any value in the range of 1 to 6; and
X comprises one or more elements selected from Li, Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al; and
the second positive electrode active material is one or more selected from LiFePO 4 , carbon-coated LiFePO 4 , LiFe d D e PO 4 , and carbon-coated LiFe d D e PO 4 , wherein D independently comprises one or more elements selected from Ti, Zn, Co, Mn, La, V, Mg, Al, Ni, W, Zr, Nb, Sm, Cr, Cu and B, d is independently selected from any value in the range of 0.99 to 0.999, and d+e=1.
2 . The positive electrode plate according to claim 1 , wherein at least one of the positive electrode film layers has a multi-layer structure, and any of the positive electrode film layers having a multi-layer structure comprises in different layers a first positive electrode active material having a core-shell structure and a second positive electrode active material and
optionally, any of the positive electrode film layers having a multi-layer structure comprises in adjacent layers the first positive electrode active material and the second positive electrode active material, respectively.
3 . The positive electrode plate according to claim 1 , comprising a positive electrode current collector and a positive electrode film layer A and a positive electrode film layer B provided on the two surfaces of the positive electrode current collector, respectively; wherein the positive electrode film layer A and the positive electrode film layer B each independently have a single-layer structure or a multi-layer structure; at least one layer of the positive electrode film layer A comprises a first positive electrode active material having a core-shell structure, and at the same time, at least one layer of the positive electrode film layer B comprises a second positive electrode active material.
4 . The positive electrode plate according to claim 1 , wherein in the second positive electrode active material,
the mass of carbon accounts for 0.1%-4% of the mass of the carbon-coated LiFePO 4 ; and/or
the mass of carbon accounts for 0.1%-4% of the mass of the carbon-coated LiFe d D e PO 4 .
5 . The positive electrode plate according to claim 1 , wherein the mass ratio of the first positive electrode active material to the second positive electrode active material is 1:7-7:1, optionally 1:4-4:1.
6 . The positive electrode plate according to claim 1 , wherein in the first positive electrode active material,
A is selected from one or more elements of Fe, Ti, V, Ni, Co and Mg, and/or
R is selected from one element of B, Si, N and S, and/or
the ratio of y to 1-y is selected from 1:10 to 1:1, optionally 1:4 to 1:1, and/or
the ratio of z to 1-z is selected from 1:9 to 1:999, optionally 1:499 to 1:249.
7 . The positive electrode plate according to claim 1 , wherein in the first positive electrode active material, the first coating layer has an interplanar spacing of the crystalline pyrophosphate in a range of 0.293-0.470 nm, and an angle of the crystal direction (111) in a range of 18.000-32.00°; and the second coating layer has an interplanar spacing of the crystalline phosphate in a range of 0.244-0.425 nm, and an angle of the crystal direction (111) in a range of 20.00°-37.00°.
8 . The positive electrode plate according to claim 1 , wherein in the first positive electrode active material, the carbon of the third coating layer is a mixture of SP2-form carbon and SP3-form carbon, and optionally, the molar ratio of the SP2-form carbon to the SP3-form carbon is any value in the range of 0.1-10, optionally any value in the range of 2.0-3.0.
9 . The positive electrode plate according to claim 1 , wherein in the first positive electrode active material,
a coating amount of the first coating layer is greater than 0 and less than or equal to 6 wt %, optionally greater than 0 and less than or equal to 5.5 wt %, more optionally greater than 0 and less than or equal to 2 wt %, based on the weight of the inner core; and/or
a coating amount of the second coating layer is greater than 0 and less than or equal to 6 wt %, optionally greater than 0 and less than or equal to 5.5 wt %, more optionally 2-4 wt %, based on the weight of the inner core; and/or
a coating amount of the third coating layer is greater than 0 and less than or equal to 6 wt %, optionally greater than 0 and less than or equal to 5.5 wt %, more optionally greater than 0 and less than or equal to 2 wt %, based on the weight of the inner core.
10 . The positive electrode plate according to claim 1 , wherein in the first positive electrode active material,
the first coating layer has a thickness of 1-10 nm; and/or
the second coating layer has a thickness of 2-15 nm; and/or
the third coating layer has a thickness of 2-25 nm.
11 . The positive electrode plate according to claim 1 , wherein in the first positive electrode active material, based on the weight of the first positive electrode active material,
a content of manganese element is in the range of 10 wt %-35 wt %, optionally in the range of 15 wt %-30 wt %, more optionally in the range of 17 wt %-20 wt %; and/or
a content of phosphorus element is in the range of 12 wt %-25 wt %, optionally in the range of 15 wt %-20 wt %; and/or
a weight ratio of manganese element to phosphorus element is in a range of 0.90-1.25, optionally 0.95-1.20.
12 . The positive electrode plate according to claim 1 , wherein the first positive electrode active material has a lattice change rate, before and after complete lithium intercalation-deintercalation, of 4% or less, optionally 3.8% or less, more optionally 2.0-3.8%.
13 . The positive electrode plate according to claim 1 , wherein the first positive electrode active material has an Li/Mn antisite defect concentration of 4% or less, optionally 2.2% or less, more optionally 1.5-2.2%.
14 . The positive electrode plate according to claim 1 , wherein the first positive electrode active material has a compacted density under 3 T of 2.2 g/cm 3 or more, optionally 2.2 g/cm 3 or more and 2.8 g/cm 3 or less.
15 . The positive electrode plate according to claim 1 , wherein the first positive electrode active material has a surface oxygen valence state of −1.90 or less, optionally −1.90 to −1.98.
16 . The positive electrode plate according to claim 1 , wherein the sum of the mass of the first positive electrode active material and the second positive electrode active material accounts for 88%-98.7% of the mass of the positive electrode plate.
17 . A secondary battery, comprising a positive electrode plate according to claim 1 .
18 . A battery module, comprising a secondary battery according to claim 17 .
19 . A battery pack, comprising a battery module according to claim 18 .
20 . A power consuming device, comprising at least one selected from a secondary battery according to claim 17 .