FR3139241A1 - Process for preparing ferromanganese phosphate by coprecipitation and its use - Google Patents

Abstract

The present invention relates to a process for preparing ferromanganese phosphate by coprecipitation and its use. The process comprises the steps of preparing a ferricyanide solution, a manganese salt solution and a mixed solution of phosphoric acid and perchloric acid respectively; adding the ferricyanide solution, the manganese salt solution, the mixed solution and the alkaline liquor to a base solution in parallel for reaction; implementation of a solid-liquid separation when the reaction mass reaches a target particle size to obtain a precipitate; and washing and drying the precipitate to obtain ferromanganese phosphate. In the present invention, the direct precipitation of trivalent ferric ions is inhibited by using ferricyanide, and perchloric acid and phosphoric acid are subjected to a cyanide breakdown reaction, thereby slowing down the precipitation rate of phosphate of iron, causes coprecipitation of iron and manganese, and improves the uniformity of the mixing of iron with manganese.

Description

Process for the preparation of ferromanganese phosphate by coprecipitation and its use

The present invention belongs to the technical field of lithium battery cathode material precursors, and particularly relates to a method for preparing ferromanganese phosphate by coprecipitation and its use.

State of the art

Lithium iron phosphate has the disadvantages of lower electronic conductivity, lower lithium ion diffusion coefficient and lower material density after material tapping in battery application. Due to the high electrochemical reaction voltage and good compatibility with electrolyte, manganese subgroup compounds are introduced into lithium iron phosphate to expand the application of lithium iron phosphate and form lithium ferromanganese phosphate solid solution, so as to achieve good electric capacity and cycle effect.

There are many methods for synthesizing lithium ferromanganese phosphate, which are basically similar to those for lithium iron phosphate. There are pure solid-state methods, including directly sintering raw materials such as a phosphorus source, an iron source, a manganese source and a lithium source, to obtain lithium ferromanganese phosphate, or first synthesizing manganese phosphate as a manganese source and forming a part of the phosphorus source, and then mixing and sintering the manganese phosphate, the iron source and the lithium source to obtain lithium ferrous manganese phosphate. The disadvantage of the existing synthesis method is that manganese and iron cannot be uniformly mixed at the atomic level, and the prepared lithium ferromanganese phosphate has a small charge constant voltage section and a low discharge performance rate. Due to the Ksp, precipitation rate and pH of manganese phosphate are different from those of iron phosphate, it is still difficult for manganese to form a co-precipitate with iron when a co-precipitation method is directly used to prepare ferromanganese phosphate. In addition, manganese in the synthesized ferromanganese phosphate mostly exists in the form of divalent manganese, and the phosphorus source still needs to be supplemented with a lithium source during the subsequent sintering. However, it is easy to have a disproportionation reaction when directly using trivalent manganese in solution, resulting in divalent manganese and tetravalent manganese, while affecting the purity of the product.

Summary

The present invention aims to solve at least one of the technical problems existing in the prior art described above. Accordingly, the present invention provides a method for preparing ferromanganese phosphate by coprecipitation and a use thereof. The method can slow down the precipitation rate of iron phosphate, so that iron and manganese can coprecipitate, and the iron and manganese in the prepared ferromanganese phosphate are uniformly distributed.

According to one aspect of the present invention, there is provided a method of preparing ferromanganese phosphate by coprecipitation, comprising the following steps:

S1, preparation respectively of a ferricyanide solution, a manganese salt solution and a mixed solution of phosphoric acid and perchloric acid;

S2, mixing the mixed solution with an alkaline liquor to obtain a base solution, introducing the ferricyanide solution, the manganese salt solution, the mixed solution and the alkaline liquor into the base solution in parallel for reaction, and carrying out solid-liquid separation when the reaction mass reaches a target particle size, to obtain a precipitate; and

S3, washing and drying the precipitate to obtain ferromanganese phosphate.

In some embodiments of the present invention, in step S1, the ferricyanide solution is a solution containing at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide or potassium ferricyanide.

In some embodiments of the present invention, in step S1, the concentration of the ferricyanide solution is 0.1 to 1.0 mol/L.

In some embodiments of the present invention, in step S1, the manganese salt in the manganese salt solution is at least one selected from the group consisting of manganese nitrate and manganese sulfate.

In some embodiments of the present invention, in step S1, the concentration of the manganese salt solution is 0.1 to 1.0 mol/L.

In some embodiments of the present invention, in step S1, the mole ratio of phosphoric acid to perchloric acid in the mixed solution is 1:(0.9 to 3.5).

In some embodiments of the present invention, in step S1, the total concentration of phosphoric acid and perchloric acid in the mixed solution is 0.5 to 1.0 mol/L.

In some embodiments of the present invention, in step S2, the pH of the base solution is 1.8 to 2.0.

In some embodiments of the present invention, in step S2, the reaction temperature is controlled at 50-70°C and the pH is adjusted to 1.8-2.0.

In some embodiments of the present invention, in step S2, the mole proportion of the ferricyanide solution, the manganese salt solution and the mixed solution is controlled to satisfy a mole ratio of Fe to Mn of (0.25 to 4):1 and a ratio of (Fe+Mn):H ₃ PO ₄ = 1:(1.02 to 1.05).

In some embodiments of the present invention, in step S2, the alkaline liquor is at least one of a sodium hydroxide solution or a potassium hydroxide solution.

In some embodiments of the present invention, in step S2, the concentration of the alkaline liquor is 0.5 to 1.0 mol/L.

In some embodiments of the present invention, in step S2, the reaction is carried out with stirring at a rotation speed of 150 to 300 rpm.

In some embodiments of the present invention, in step S2, the target particle size D50 is 2 to 15 µm.

In some embodiments of the present invention, in step S3, the drying is vacuum drying at a temperature of 120 to 150°C for 2 to 4 hours.

The present invention further provides the use of the method for preparing a lithium ferromanganese phosphate or a lithium ion battery.

According to a preferred embodiment of the present invention, at least the following advantageous effects are provided:

1. In the present invention, ferricyanide and manganese salt are subjected to a coprecipitation reaction in a medium of phosphoric acid and perchloric acid, so as to produce co-precipitates of ferromanganese phosphate. The reaction equation is as follows (taking sodium ferricyanide as an example):

4Na ₃ [Fe(CN) ₆ ]+15HClO ₄ +4H ₃ PO ₄ →24CO ₂ ↑+12N ₂ ↑+12NaCl+12H ₂ O+4FePO ₄ ↓+3HCl ;

14Mn ²⁺ +14H ₃ PO ₄ +2HClO ₄ →14MnPO ₄ ↓+Cl ₂ ↑+8H ₂ O+28H ⁺ .

2. In the present invention, when preparing ferromanganese phosphate, on the one hand, both iron and manganese are co-precipitated with phosphate radicals in the positive trivalent state to form ferromanganese phosphate, which avoids the subsequent problem that a phosphorus source is insufficient due to the precipitation of divalent cations and needs to be supplemented, and avoids uneven distribution of phosphorus, manganese and iron. On the other hand, due to the large difference in Ksp between iron phosphate and manganese phosphate, it is difficult for iron to co-precipitate directly with manganese. In the present invention, the direct precipitation of trivalent ferric ions is inhibited by using ferricyanide, and perchloric acid and phosphoric acid are subjected to a cyanide cleavage reaction, thereby slowing down the precipitation rate of iron phosphate, co-precipitating iron and manganese, improving the mixing uniformity of iron with manganese, and the bottom is deposited for subsequent sintering of a lithium ferromanganese phosphate cathode material to improve the specific capacity of the material and the cycle performance.

Brief description of the figures

The present invention will be described in more detail with reference to the accompanying drawings and the following examples, in which:

There is a scanning electron microscope (SEM) image of ferromanganese phosphate prepared according to Example 1 of the present invention.

The concept and technical effects of the present invention will be clearly and fully described below with reference to examples, so as to fully understand the objects, features and effects of the present invention. Of course, the examples described only form a part, and not the whole, of the examples of the present invention. All other examples obtained by the person skilled in the art on the basis of the examples of the present invention without creative effort will fall within the scope of protection of the present invention.

Example 1

In this example, ferromanganese phosphate was prepared. The specific procedure was as follows:

Step 1, a sodium ferricyanide solution with a concentration of 1.0 mol/L was prepared;

Step 2, a manganese nitrate solution with a concentration of 1.0 mol/l was prepared;

Step 3, a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/L was prepared, at a mole ratio of phosphoric acid to perchloric acid of 1:2;

Step 4, a sodium hydroxide solution with a concentration of 1.0 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction vessel, and used as a base solution, the base solution submerging a bottom stirring blade, and the pH being 1.8 to 2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole ratio of the materials introduced into the reaction vessel was controlled to have a mole ratio of Fe to Mn of 1:1, and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1, and the pH in the reaction vessel was adjusted to 1.8-2.0, at a stirring speed of 250 rpm and a reaction temperature of 70 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 10.5 µm, the introduction was stopped, and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 135°C for 3 hours to obtain a ferromanganese phosphate product.

Example 2

In this example, a ferromanganese phosphate was prepared. The specific procedure was as follows:

Step 1, a potassium ferricyanide solution with a concentration of 0.5 mol/l was prepared;

Step 2, a manganese sulfate solution with a concentration of 0.5 mol/l was prepared;

Step 3, a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/l was prepared, for a mole ratio of phosphoric acid to perchloric acid of 1:0.9;

Step 4, a sodium hydroxide solution with a concentration of 0.5 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction tank and used as a base solution, with the base solution overflowing from the bottom stirring blade, and the pH being 1.8 to 2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole proportion of the materials introduced into the reaction vessel was controlled so as to have a mole ratio of Fe to Mn of 0.25:1 and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1; and the pH in the reaction vessel was adjusted to 1.8-2.0, with a stirring speed of 300 rpm, and the reaction temperature was 60 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 2 µm, the introduction was stopped and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 120°C for 4 hours to obtain a ferromanganese phosphate product.

Example 3

In this example, a ferromanganese phosphate was prepared. The specific procedure was as follows:

Step 1, a sodium ferrocyanide solution with a concentration of 0.1 mol/l was prepared;

Step 2, a manganese nitrate solution with a concentration of 0.1 mol/l was prepared;

Step 3, a mixed solution of phosphoric acid and perchloric acid was prepared with a total concentration of 0.5 mol/l, for a mole ratio of phosphoric acid to perchloric acid of 1:3.5;

Step 4, a sodium hydroxide solution with a concentration of 0.5 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction tank and used as a base solution, the base solution overflowing from a bottom stirring blade, and the pH was 1.8-2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole ratio of the materials introduced into the reaction vessel was controlled so as to have a mole ratio of Fe to Mn of 1:1 and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1; and the pH in the reaction vessel was adjusted to 1.8-2.0, at a stirring speed of 150 rpm and a reaction temperature of 50 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 15 µm, the introduction was stopped and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 150°C for 2 hours to obtain a ferromanganese phosphate product.

Comparative example 1

In this comparative example, a ferromanganese phosphate was prepared. Comparative Example 1 differed from Example 1 in that the iron source used was ferric nitrate. The specific procedure was as follows:

Step 1, a ferric nitrate solution with a concentration of 1.0 mol/l was prepared;

Step 2, a manganese nitrate solution with a concentration of 1.0 mol/l was prepared;

Step 3, a mixed solution of phosphoric acid and perchloric acid with a total concentration of 1.0 mol/l was prepared, for a mole ratio of phosphoric acid to perchloric acid of 1:2;

Step 4, a sodium hydroxide solution with a concentration of 1.0 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction vessel and used as a stock solution, with the stock solution overflowing from a bottom stirring paddle, for a pH of 1.8 to 2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole ratio of the materials introduced into the reaction vessel was controlled so as to have a mole ratio of Fe to Mn of 1:1 and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1; and the pH in the reaction vessel was adjusted to 1.8-2.0, at a stirring speed of 250 rpm and a reaction temperature of 70 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 10.5 µm, the introduction was stopped, and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 135°C for 3 hours to obtain a ferromanganese phosphate product.

Comparative example 2

In this comparative example, a ferromanganese phosphate was prepared. Comparative Example 2 differed from Example 2 in that the iron source used was ferric sulfate. The specific procedure was as follows:

Step 1, a ferric sulfate solution with a concentration of 0.5 mol/l was prepared;

Step 2, a manganese sulfate solution with a concentration of 0.5 mol/l was prepared;

Step 3, a mixed solution of phosphoric acid and perchloric acid was prepared with a total concentration of 1.0 mol/l for a mole ratio of phosphoric acid to perchloric acid of 1:0.9;

Step 4, a sodium hydroxide solution with a concentration of 0.5 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction vessel and used as a stock solution, with the stock solution overflowing from a bottom stirring paddle, for a pH of 1.8-2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole ratio of the materials introduced into the reaction vessel was controlled so as to have a mole ratio of Fe to Mn of 0.25:1 and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1; and the pH in the reaction vessel was adjusted to 1.8-2.0, at a stirring speed of 300 rpm and a reaction temperature of 60 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 2 µm, the introduction was stopped, and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 120°C for 4 hours to obtain a ferromanganese phosphate product.

Comparative example 3

In this comparative example, a ferromanganese phosphate was prepared. Comparative Example 3 differed from Example 3 in that the iron source used was ferrous nitrate. The specific procedure was as follows:

Step 1, a ferrous nitrate solution with a concentration of 0.1 mol/l was prepared;

Step 2, a manganese nitrate solution with a concentration of 0.1 mol/l was prepared;

Step 3, a mixed solution of phosphoric acid and perchloric acid was prepared with a total concentration of 0.5 mol/l, for a mole ratio of phosphoric acid to perchloric acid of 1:3.5;

Step 4, a sodium hydroxide solution with a concentration of 0.5 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction vessel and used as a stock solution, with the stock solution overflowing from a bottom stirring paddle, for a pH of 1.8-2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole proportion of the materials introduced into the reaction vessel was controlled so as to have a mole ratio of Fe to Mn of 4:1 and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1; and the pH in the reaction vessel was adjusted to 1.8-2.0, at a stirring speed of 150 rpm and a reaction temperature of 50 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 15 µm, the introduction was stopped, and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 150°C for 2 hours to obtain a ferromanganese phosphate product.

Comparative example 4

In this comparative example, a ferromanganese phosphate was prepared. Comparative Example 4 was different from Example 1 in that the iron source used was ferric nitrate, and perchloric acid was not added. The specific procedure was as follows:

Step 1, a ferric nitrate solution with a concentration of 1.0 mol/l was prepared;

Step 2, a manganese nitrate solution with a concentration of 1.0 mol/l was prepared;

Step 3, a phosphoric acid solution with a concentration of 1.0 mol/l was prepared;

Step 4, a sodium hydroxide solution with a concentration of 1.0 mol/l was prepared;

Step 5, the solutions prepared in step 3 and step 4 were introduced into a reaction vessel and used as a stock solution, with the stock solution overflowing from a bottom stirring paddle, for a pH of 1.8-2.0;

Step 6, the solutions prepared in step 1, step 2, step 3 and step 4 were introduced into the reaction vessel in parallel; the mole proportion of the materials introduced into the reaction vessel was controlled so as to have a mole ratio of Fe to Mn of 1:1 and a ratio of (Fe+Mn):H ₃ PO ₄ of 1:1; and the pH in the reaction vessel was adjusted to 1.8-2.0, at a stirring speed of 250 rpm and a reaction temperature of 70 °C;

Step 7, when the D50 of the material in the reaction vessel was detected to be 10.5 µm, the introduction was stopped, and solid-liquid separation was carried out to obtain precipitates;

Step 8, the precipitates were first washed with deionized water and then washed with anhydrous ethanol; and

Step 9, the product obtained after washing was dried under vacuum at 135°C for 3 hours to obtain a ferromanganese phosphate product.

The ferromanganese phosphate products obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were tested by ICP, and the results are shown in Table 1.

Fe/% Mn/% P/% Fe:Mn:P Gross chemical formula Example 1 18,566 18,270 20,601 0.5:0.5:1 Fe _0.5 Mn _0.5 PO ₄ Example 2 7,442 29,281 20,637 0.2:0.8:1 Fe _0.2 Mn _0.8 PO ₄ Example 3 18,568 18,267 20,603 0.5:0.5:1 Fe _0.5 Mn _0.5 PO ₄ Comparative example 1 32,602 4,377 20,552 0.88:0.12:1 Fe _0.88 Mn _0.12 PO ₄ Comparative example 2 32,606 4,377 20,553 0.88:0.12:1 Fe _0.88 Mn _0.12 PO ₄ Comparative example 3 32,605 4,378 20,553 0.88:0.12:1 Fe _0.88 Mn _0.12 PO ₄ Comparative example 4 36,234 1,068 20,459 1:0.03:1.02 FePO ₄ ·0.01Mn ₃ (PO ₄ ) ₂

It can be seen from the test results in Table 1 that the amount of manganese precipitation in each of the comparative examples is very small. Even if the amount of manganese is increased to the maximum, the amount of manganese precipitation is still very small, and the desired ferromanganese phosphate product cannot be obtained.

Sample test

For a mole ratio of (Fe+Mn): Li: carbon source of 1:1.1:0.4, the ferromanganese phosphate products obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were mixed with lithium hydroxide and glucose respectively, deionized water was added to a total mass of 25%, spray drying was carried out after mixing until uniform, and the obtained dried mixture was calcined at 750°C for 16 hours under the protection of an inert gas, subjected to natural cooling to room temperature to obtain a finished lithium ferromanganese phosphate cathode material.

The lithium ferromanganese phosphate cathode materials obtained in the Examples and Comparative Examples were mixed with acetylene black as a conductive agent and PVDF as a binder at a mass proportion of 8:1:1, an appropriate amount of the organic solvent NMP was added for stirring, a mixed solution was applied to an aluminum foil to prepare a positive electrode plate. An A2023 button cell comprising the above positive electrode plate, a negative electrode made of a lithium metal plate, a diaphragm made of a Celgard2400 polypropylene porous membrane, an electrolyte comprising a solvent consisting of EC, DMC and EMC at a mass proportion of 1:1:1 and a LiPF ₆ solute having a concentration of 1.0 mol/L was assembled in a glove box. The charge-discharge cycle performance of the cell was tested, the specific discharge capacities at 0.2C and 1C were tested at a cut-off voltage between 2.2 V and 4.3 V. The results of the electrochemical performance tests are shown in Table 2.

Discharge capacity at 0.2C (mAh/g) Discharge capacity at 0.1C (mAh/g) Capacity retention rate for 600 times at 1C (%) Example 1 151.3 143.7 95.56% Example 2 153.2 141.2 93.07% Example 3 151.8 143.3 95.05% Comparative example 1 143.5 122.1 85.09% Comparative example 2 147.6 124.6 84.42% Comparative example 3 144.2 123.3 85.51% Comparative example 4 132.6 106.9 80.62%

It can be seen from Table 2 that the electrochemical performance of the examples is obviously better than that of the comparative examples, indicating that the lithium ferromanganese phosphate obtained by sintering the ferromanganese phosphate prepared by the present invention has a large specific capacity and a high cycle performance.

The examples of the present invention have been described in detail with reference to the drawings attached above, but the present invention is not limited to the above examples. Various modifications may be made within the scope of the knowledge of a person skilled in the art without departing from the subject matter of the present invention. Furthermore, the examples of the present invention and the features given in the examples may be combined with each other without conflict.

Claims (10)

A process for the preparation of ferromanganese phosphate by coprecipitation, comprising the following steps:
S1, preparation of a ferricyanide solution, a manganese salt solution and a mixed solution of phosphoric acid and perchloric acid respectively;
S2, mixing the mixed solution with an alkaline liquor to obtain a base solution, adding the ferricyanide solution, the manganese salt solution, the mixed solution and the alkaline liquor to the base solution in parallel for a reaction, and carrying out solid-liquid separation when a reaction mass reaches a target particle size to obtain a precipitate; and
S3, washing and drying the precipitate to obtain ferromanganese phosphate. Method according to claim 1,
wherein in step S1, the ferricyanide solution is a solution containing at least one of sodium ferrocyanide, potassium ferrocyanide, sodium ferricyanide or potassium ferricyanide. Method according to claim 1,
wherein in step S1, a concentration of the ferricyanide solution is 0.1 to 1.0 mol/l. Method according to claim 1,
wherein in step S1, the manganese salt in the manganese salt solution is at least one selected from the group consisting of manganese nitrate and manganese sulfate. Method according to claim 1,
wherein in step S1, a mole ratio of phosphoric acid to perchloric acid in the mixed solution is 1:(0.9 to 3.5). Method according to claim 1,
wherein in step S2, a pH value of the base solution is 1.8-2.0. Method according to claim 1,
wherein in step S2, a reaction temperature is controlled at 50 to 70°C, and the pH value is adjusted to 1.8-2.0. Method according to claim 1,
wherein in step S2, a mole ratio of the ferricyanide solution, the manganese salt solution and the mixed solution is regulated to satisfy: a mole ratio of Fe to Mn is (0.25 to 4):1, and (Fe + Mn):H ₃ PO ₄ = 1:(1.02 to 1.05). Method according to claim 1,
wherein in step S2, the alkaline liquor is at least one of a sodium hydroxide solution and a potassium hydroxide solution. Use of the process according to any one of claims 1 to 9 in the preparation of a lithium-ferromanganese phosphate or lithium-ion battery.